Ethylenic silicon compounds and thermoplastic elastomers obtained therefrom

ABSTRACT

The invention provides organosilicon compounds of the formula: ##STR1## in which: N IS 1, 2 OR 3; 
     Each R, which may be identical or different, is a monovalent organic group which contains a carbon-carbon double bond and from 2 to 10 carbon atoms; 
     Each R 1 , which may be identical or different, is a straight or branched alkyl radical optionally substituted by one or more halogen atoms or cyano groups; an aryl radical or an alkylaryl radical optionally substituted by one or more halogen atoms; 
     R 2  is a straight or branched divalent alkylene or alkylidene radical possessing up to 4 carbon atoms; 
     X is a divalent radical consisting of, or containing, at least one hetero-atom selected from oxygen, sulphur and nitrogen atoms, the radical being attached to the radical R 2  via a said hetero-atom; 
     G is an organic radical of valency (m+ l) possess from 1 to 30 carbon atoms; 
     m is 1, 2 or 3; 
     And each Y, which may be identical or different, is a functional group selected from: --NO 2 , ##STR2## --COOM (where M represents a sodium, potassium or lithium atom); --COOR 4  ; ##STR3## --COCl; --OH; --OR 4  ; ##STR4## --SH; --SR 4  ; ##STR5## --CONH 2  ; --CSNH 2  ; --CN; --CH 2  --NH 2  ; --CHO; ##STR6## --NCO; ##STR7## wherein R 3  represents a hydrogen atom or a straight or branched alkyl radical possessing up to 6 carbon atoms and R 4  represents an alkyl radical possessing up to 4 carbon atoms, with the proviso that two Y groups can together constitute an imide group ##STR8## wherein R 5  represents a hydrogen atom or a straight or branched alkyl radical possessing up to 4 carbon atoms. 
     These are useful intermediates in the preparation of disilanes and silicon polymers, in particular of polyethylenic silicon compounds which can be polymerized with an α, ω-dihydrogenopolysiloxane to give thermoplastic elastomers.

The present invention relates to ethylenic silicon compounds containingat least one functional group other than the ethylenic double bond,polyethylenic silicon compounds with carbo-functional units andthermoplastic elastomers with carbo-functional units obtained from thelatter.

The value of silicon compounds containing at least two functional groupsis well known because such compounds open the way to organo-siliconpolymers and copolymers. Thus, bis-(carboxyphenyl)-dimethylsilane andbis-(carboxyphenyl)-tetramethyldisiloxane have been described. Thesecompounds have been used to prepare polyamides and polyesters (see, forexample, U.S. Pat. No. 2,754,284).

A. More specifically, a first subject of the present invention are theethylenic compounds of the general formula: ##STR9## and the process bywhich they may be obtained.

In the formula (I) each symbol represents:

n: an integer which may have the value 1, 2 or 3.

R: identical or different monovalent organic groups which contain anethylenic double bond and comprise from 2 to 10 carbon atoms.

R₁ : identical or different straight or branched alkyl radicalsoptionally substituted by one or more halogen atoms or by one or morecyano groups; aryl radicals and alkylaryl radicals, these radicals beingoptionally substituted by one or more halogen atoms.

R₂ : a straight or branched divalent alkylene or alkylidene radicalpossessing from 1 to 4 carbon atoms.

X: a divalent radical consisting of, or containing, at least onehetero-atom O, S or N, this radical X being attached to the radical R₂via a said hetero-atom.

G: an organic radical of valency (m + l) possessing from 1 to 30 carbonatoms.

m: an integer which assumes the values 1, 2 and 3.

Y: identical or different functional groups chosen from the list of thefollowing groups: ##STR10## --COOM (where M represents a sodium,potassium or lithium atom); ##STR11## The radical R₃ represents ahydrogen atom or a straight or branched alkyl radical possessing from 1to 6 carbon atoms and R₄ represents a straight or branched alkyl radicalpossessing from 1 to 4 carbon atoms. Furthermore, two groups Y cantogether constitute an imide group ##STR12## wherein R₅ represents ahydrogen atom or a straight or branched alkyl radical having from 1 to 4carbon atoms.

More precisely, the various preceding symbols suitably assume thefollowing meanings:

I - RADICAL R:

This radical represents a straight or branched alkenyl group optionallysubstituted by one or more halogen atoms, or a cycloalkenyl groupoptionally substituted by one or more halogen atoms. In this contextthere may be mentioned straight or branched alkenyl groups having from 2to 6 carbon atoms and optionally substituted by one to three atoms ofchlorine and/or of fluorine, such as the following groups: vinyl, allyl,2,2-dichlorovinyl, 1,2,2-trichlorovinyl, prop-2-enyl, but-2-enyl,prop-1-enyl, but-1-enyl and 2-methyl-prop-1-enyl.

R can also represent a monovalent group of the formula ##STR13## inwhich: the symbols X₁, X₂ and X₃ independently represents a hydrogenatom or a straight or branched alkyl group having from 1 to 4 carbonatoms, such as the methyl, ethyl and isobutyl radicals, or a phenylgroup; X₄ denotes one of the following organosilicon groups: ##STR14##wherein the radicals R₆, which may be identical or different, representa methyl or phenyl group and n₁ is an integer equal to 1, 2 or 3.

Preferably R represents a linear alkenyl group having from 2 to 6 carbonatoms.

II - RADICAL R₁

It represents, more specifically:

Straight or branched alkyl groups having at most 10 carbon atoms andoptionally substituted by one to four atoms of chlorine and/or fluorineor by a cyano group, or aryl groups such as phenyl, or alkylaryl groupscontaining from 1 to 4 carbon atoms in the alkyl substituent, such astolyl radicals; these aromatic radicals are optionally substituted byone to four atoms of chlorine and/or fluorine.

Amongst these radicals there may be mentioned the following groups:methyl, ethyl; propyl; isopropyl; butyl; isobutyl; α-pentyl; t-butyl;chloromethyl; dichloromethyl; α-chloroethyl; α,β-dichloroethyl;fluoromethyl; difluoromethyl; α,β-difluoroethyl; 3,3,3-trifluoropropyl;4,4,4-trifluorobutyl; 3,3,4,4,5,5-heptafluoropentyl; β-cyanoethyl;γ-cyanopropyl; phenyl; p-chlorophenyl; m-chlorophenyl;3,5-dichlorophenyl; trichlorophenyl; tetrachlorophenyl; o-, p- orm-tolyl; α,α,α-trifluorotolyl; and xylyl groups such as2,3-dimethylphenyl and 3,4-dimethylphenyl.

The radical R₁ preferentially represents an alkyl radical having from 1to 5 carbon atoms optionally substituted by 1 to 4 atoms of chlorineand/or fluorine, or a phenyl radical.

III - RADICAL R₂

This radical represents a divalent radical defined above such asmethylene, ethylene, trimethylene, ethylidene, tetramethylene,isopropylidene and methylethylene.

Preferably, R₂ represents a methylene or ethylene group.

IV - RADICAL X

This radical suitably represents one of the following groups linked bythe hetero-atom to the radicals R₂ : ##STR15## wherein R₅ has themeaning given above.

X preferentially represents an oxygen atom or sulphur atom or a##STR16## group (wherein R₅ represents a hydrogen atom or a methyl orethyl radical).

V - RADICAL G

It suitably represents the following divalent, trivalent or tetravalentradicals:

1. A hydrocarbon radical which may be saturated or unsaturated, straightor branched, aliphatic or cycloaliphatic, optionally substituted by oneor more chlorine atoms; a monocyclic or polycyclic aromatic radicaloptionally substituted by one or more methyl radicals and/or one or morechlorine atoms, it being possible for these aromatic radicals to form,with each other, ortho-condensed, or ortho- and peri-condensed systems.

2. A saturated or unsaturated or aromatic, monocyclic or polycyclicheterocyclic radical containing at least one of the hetero-atoms O, Nand S, this heterocyclic radical optionally being substituted by methylradicals.

The term "polycyclic heterocyclic radical" denotes a radical containingat least two heterocyclic structures or at least one heterocyclicstructure combined with at least one aromatic or non-aromatichydrocarbon ring, the whole forming an ortho-condensed or ortho- andperi-condensed system. This meaning is intended throughout thisSpecification.

3. A radical consisting of a chain of several divalent alkylene and/orcycloalkylene and/or arylene and/or heterocyclic radicals, linked to oneanother by a valency bond and/or by at least one of the followingdivalent groups: ##STR17## (wherein R₇ and R₈ independently represent analkyl radical having from 1 to 4 carbon atoms such as methyl, ethyl,n-propyl and n-butyl; a cyclohexyl radical or a phenyl radical, and R₇can also represent a hydrogen atom), and/or by an alkylene or alkylidenegroup having from 1 to 4 carbon atoms, such as methylene, ethylene andisopropylidene.

Amongst the radicals which have just been mentioned, G more particularlyrepresents the following divalent and trivalent radicals: a) a straightor branched alkylene, alkylidene, alkenylene or alkenylidene radicalhaving from 1 to 12 carbon atoms or a cycloalkylene or cycloalkenyleneradical having from 5 to 8 nuclear carbon atoms.

By way of illustration, the following radicals may be mentioned:methylene; ethylene; propylene; butylene; hexamethylene; cyclohexylene.

b. An arylene radical such as m-phenylene; p-phenylene; toluylene, suchas 5-methyl-1,3-phenylene and 2-methyl-1,4-phenylene; a xylylene radicalsuch as 1,2-dimethyl-3,6-phenylene; naphthylene; anthracenylene.

c. A heterocyclic, saturated or unsaturated or aromatic radicalcontaining one or more hetero-atoms O, N and S and 4 to 6 atoms in thering, optionally substituted by one or two methyl groups.

The following radicals may be mentioned by way of illustration:##STR18##

d. A divalent radical consisting of a chain of 2 to 4 groups chosen fromamongst those defined under a) and/or b) and/or c), linked to oneanother by a valency bond and/or by at least one of the groups ##STR19##and/or by an alkylene and/or alkylidene group having from 1 to 4 carbonatoms, such as those already mentioned.

As examples of such groups, the following radicals may be mentioned:##STR20##

Preferably, G represents an alkylene or alkylidene radical having from 1to 6 carbon atoms; a cyclohexylene radical; a m- or p-phenylene radical;toluylene; xylylene; a radical formed by two phenylene groups linked toone another by a valency bond or by an alkylene or alkylidene grouphaving from 1 to 4 carbon atoms (such as methylene; ethylene; propylene;isopropylidene); an oxygen atom; one of the following groups: ##STR21##

e. A trivalent radical such as:

a benzenetriyl radical such as 1,2,4-benzenetriyl,

a naphthalenetriyl radical such as 2,3,6-naphthalenetriyl, and

a radical of the formula ##STR22## in which E represents a valency bondor an alkylene or alkylidene group having from 1 to 4 carbon atoms, suchas those already mentioned, or one of the following groups: ##STR23##

Amongst the trivalent groups G more preferentially represents thefollowing groups: ##STR24##

Preferably in the compounds of the formula (I) the various symbols havethe following meanings:

n is an integer equal to 1 or 2,

R is a linear alkenyl group having from 2 to 6 carbon atoms, andespecially a vinyl or allyl radical,

R₁ is an alkyl group having from 1 to 5 carbon atoms, optionallysubstituted by 1 to 4 atoms of chlorine and/or fluorine, or a phenylgroup,

R₂ is a methylene or ethylene group and

X is one of the following groups: ##STR25## (wherein R₅ represents ahydrogen atom or a methyl radical).

G: a straight or branched alkylene radical having from 1 to 6 carbonatoms; a cyclohexylene radical; a phenylene, p-tolylene or xylyleneradical; benzylene; a divalent radical consisting of two phenylenenuclei linked to one another by a valency bond or by one of thefollowing groups: a methylene or isopropylidene group or --O--, --NH--,--SO₂ --, --CO-- or --CO--NH--; a trivalent radical such as thebenzenetriyl radical or one of the following radicals: ##STR26##

The following compounds of the formula (I) may be mentioned by way ofillustration: 1-nitro-4-(vinyldimethylsilylmethoxy)-benzene,1-nitro-(2-vinyldimethylsilyl-ethoxy)benzene,1-nitro-(3-vinyldimethylsilyl-propoxy)-benzene,1-methoxycarbonyl-4-(vinyldimethylsilylmethoxy)-benzene,1-ethoxycarbonyl-4-(vinyldimethylsilylmethoxy)-benzene,1-carboxy-4-(vinyldimethylsilylmethoxy)-benzene,1-amino-4-(vinyldimethylsilylmethoxy)-benzene,1-amino-4-(vinyldimethylsilylmethoxycarbonyl)-benzene,1-ethoxycarbonyl-4-(allyldimethylsilylmethoxy)-benzene,1-nitro-4-(methyldivinylsilylmethoxy)-benzene,1-methoxycarbonyl-4-(2-methyldivinylsilylethoxy)-benzene,1-nitro-4-(vinyldiphenylsilylmethoxy)-benzene,1-nitro-[vinyl-bis(3,4-dichlorophenyl)silylmethoxy]-benzene,1-nitro-4-(allyldimethylsilylmethoxy)-benzene,1-nitro-4-[(but-1-enyl)dimethylsilylmethoxy]-benzene,1-nitro-4-[(dimethylvinylsiloxy)dimethylsilylmethoxy]-benzene,1-nitro-4-[(1,2,2-trichlorovinyl)dimethylsilylmethoxy]-benzene,1-nitro-4-(methylphenylvinylsilylmethoxy)-benzene,1-nitro-4-(methyl-γ-cyanopropylvinylsilylmethoxy)-benzene,1,2-dinitro-4-(vinyldimethylsilylmethoxy)-benzene, the ethyl ester of4-(vinyldimethylsilylmethoxy)-butanoic acid, the ethyl ester of2-(vinyldimethylsilylmethoxy)-acetic acid,3-ethoxycarbonyl-4-(vinyldimethylsilylmethoxy)-pyridine,1-ethoxycarbonyl-4-(vinyldimethylsilylmethylthio)-benzene,1-nitro-4-(vinyldimethylsilylmethylthio)-benzene,1-nitro-4-(allyldimethylsilylmethylthio)-benzene,1-nitro-4-(vinyldimethylsilylmethoxycarbonyl)-benzene,1-ethoxycarbonyl-4-(vinyldimethylsilylethoxycarbonyl)-benzene,1-ethoxycarbonyl-4-(allyldimethylsilylmethoxycarbonyl)-benzene,1-ethoxycarbonyl-4-(vinyldimethylsilylmethoxycarbonyl)-benzene,1-ethoxycarbonyl-4-(vinyldimethylsilylmethylthiocarbonyl)-benzene,1-ethoxycarbonyl-4-(vinyldimethylsilylmethylthio-thiocarbonyl)-benzene,the ethyl ester of 2-(vinyldimethylsilylmethyl)-thioglycollic acid,N-p-nitrophenyl,N-vinyldimethylsilylmethylmethylamine,N-p-ethoxycarbonylphenyl,N-vinyldimethylsilylmethyl-methylamine,1-chlorocarbonyl-4-(vinyldimethylsilylmethoxy)-benzene,1-amino-4-(vinyldimethylsilylmethoxycarbonyl)-benzene,1-carboxy-4-(vinyldimethylsilylmethoxycarbonyl)-benzene,1-cyano-4-(vinyldimethylsilylmethoxycarbonyl)-benzene,1-ethoxy-4-(vinyldimethylsilylmethoxycarbonyl)-benzene,1-isocyanato-4-(vinyldimethylsilylmethoxy)-benzene,1-aminomethyl-4-(vinyldimethylsilylmethoxy)-benzene,1,2-bis-methoxycarbonyl-4-(vinyldimethylsilylmethoxy)-benzene,1,2-bis-methoxycarbonyl-4-(vinyldimethylsilylmethoxy-carbonyl)-benzene,4-vinyldimethylsilylmethoxy-4'-ethoxy-diphenylmethane,4-vinyldimethylsilylmethoxy-4'-nitro-diphenylmethane,4-vinyldimethylsilylmethoxy-4'-methoxycarbonyl-diphenylmethane,4-vinyldimethylsilylmethoxy-4'-methoxycarbonyl-diphenylsulphone,4-vinyldimethylsilylmethoxy-4'-methoxycarbonyl-diphenyl ether,4-vinyldimethylsilylmethoxycarbonyl-4'-methoxycarbonyl-diphenylmethane,N-methyl-4-(vinyldimethylsilylmethoxy)-phthalimide,1-methoxycarbonyl-4-(divinylmethylsilylmethoxy)-benzene,1-chlorocarbonyl-4-(divinylmethylsilylmethoxy)-benzene and4-(divinylmethylsilylmethoxy)-benzoic acid.

The organo-silicon compounds (I) can be obtained according to a processwhich consists of reacting:

a. an organo-silicon compound (II) containing a chloroalkyl group andhaving the formula: ##STR27## with

b. a compound of the formula (III)

    z -- x -- g (y.sub.1).sub.m ]                              (III)

in which Z represents a hydrogen atom, an alkali metal or an ammoniumgroup of the formula

    [(R.sub.9).sub.3 NH--

where R₉ represents an alkyl group having from 1 to 4 carbon atoms. Thesymbol Y₁ represents a functional group such as those defined above forY, but Y₁ is a functional group which is inert during the reaction.

If X represents an oxygen atom, a sulphur atom or a carboxyl orthiocarboxyl group, Z is preferably a sodium, potassium or lithium atom,or an ammonium group [(R₉)₃ NH--. For convenience, the alkali metalsalts and the tertiary amine salts of the acids or of the phenols havebeen represented by a formula which uses covalent bonds. Obviously,these compounds can be employed in the ionic form.

If X represents a ##STR28## group, Z is preferably H.

As has just been seen, the process according to the invention consistsof reacting, by bringing into contact, an organo-silicon compound havinga chloroalkyl group with a compound such as a phenate, carboxylate,thiocarboxylate, thiolate or amine. The amine compound can optionally beused in the form of its hydrochloride.

As has been indicated, the functional group Y₁ is a group which is inertduring the condensation reaction. This group Y₁ must not be able toreact with the chloroalkyl group of the silicon derivative or with theZ--X-- group. Equally, this group Y₁ must not be able to react withanother group Y. The nature of the radicals Y₁ can easily be deduced bythose skilled in the art from the nature of the compounds (II) and(III). The compounds (I) obtained directly from the organo-siliconcompounds with chloroalkyl groups and the compounds Z--X--G(Y₁)_(m) ]will hereafter be referred to as compounds (Ia).

By way of indication, if Z--X-- represent a group containing an alkalimetal atom or a quaternary ammonium group, Y₁ can be one of thefollowing functional groups: ##STR29##

If Z--X-- represents an amino group, the group Y₁ can be ##STR30##

Starting from the compounds (Ia) defined above, it is possible toobtain, in accordance with the conventional methods of organicchemistry, other compounds (I), referred to as (Ib), which containfunctional groups Y different from the Y₁ groups and which are by naturecapable of reacting with one of the following groups: chloroalkyl,Z--X-- or a Y₁ group. These compounds (Ib) contain, for example, Ygroups such as --COCl; --NCO; --CHO. For example, the nitro derivativescan be converted to their corresponding amine or isocyanato derivatives.It is also possible to obtain the corresponding acids and acidchlorides.

The organo-silicon compounds (II) can be obtained in accordance with thegeneral methods for obtaining organo-silicon derivatives havingchloroalkyl groups. For this purpose, it is usual to preparechloroalkylchlorosilanes, which are converted by a Grignard reaction tothe corresponding ethylenic organo-silicon compounds. These methods aredescribed, for example, in the treatise by Eaborn: OrganosiliconCompounds, p. 379-381 (1960).

Purely by way of illustration, the following compounds may be mentionedamongst the organo-silicon compounds (II):vinyldimethylchloromethylsilane, allyldimethylchloromethylsilane,methyldivinylchloromethylsilane, vinyldiphenylchloromethylsilane,allyldiphenylchloromethylsilane, vinyldimethylchloroethylsilane,vinyldimethyl-n-chloropropylsilane,but-1-enyl-dimethylchloromethylsilane,1,2,2-trichlorovinyldimethylchloromethylsilane,vinylmethylphenylchloromethylsilane,γ-cyanopropyl-vinylmethylchloromethylsilane, and1,1,3,3-tetramethyl-3-vinyl-1-chloromethyl-disiloxane.

The compounds of the formula (III) can be amine compounds such asp-ethoxycarbonylphenylmethylamine, p-nitrophenylmethylamine andN-methyl-4-amino-4'-nitrodiphenylmethane, or alkali metal salts ortertiary amine salts of carboxylic or thiocarboxylic acids such asp-methoxybenzoic acid, the monoethyl ester of terephthalic acid, themonomethyl ester of diphenylmethane-4,4'-dicarboxylic acid, p- orm-nitrobenzoic acid, 3,4-dinitrobenzoic acid and p-nitrothiobenzoicacid.

These compounds (III) can also be alkali metal alcoholates or thiolatessuch as the salts of the following compounds: methyl p-hydroxybenzoate;p-hydroxynitrobenzene; 4-hydroxy-4'-nitro-diphenylmethane;4-hydroxy-4'-ethoxydiphenyl ether; ethyl 4-mercapto-benzoate;4-mercapto-nitrobenzene; 4-mercapto-ethoxybenzene; the ethyl ester ofthioglycollic acid; the methyl ester of 4-hydroxy-butanoic acid.

The condensation reactions of the organo-silicon compound (II) and ofthe compound (III) can be carried out in accordance with the generalprocesses described in the literature relating to the nucleophilicsubstitution reactions which employ an organo-silicon compound with achloroalkyl group; [see, e.g., Eaborn; Organosilicon Compounds, p.393;411; 412; 413 (1960) and U.S. Pat. Nos. 2,783,262; 2,783,263 and2,833,802].

As a general rule, the condensation reaction is carried out at atemperature of between 0° and 150° and preferably between 20° and 100°C, by gradually introducing one of the reactants into the reactionmedium containing the other reactant. In general, the reaction iscarried out in a solvent medium consisting of alcohols, such as methanolor ethanol, polar aprotic solvents such as N-methylpyrrolidone,dimethylformamide, dimethylacetamide and hexamethylphosphotriamide, ororganic ethers, such as the methyl ether of diglycol. Once the reactionhas been completed, the compounds (I) are isolated from the reactionmedium by any known means such as, for example, distillation orfractional crystallisation.

The compounds according to the invention are very valuable synthesisintermediates in organo-silicon chemistry by virtue of the simultaneouspresence in their molecule of an ethylenic group and of at least oneother functional group. Thus it is possible, for example, to add ontothe ethylenic double bond a hydrogenosilane which itself carries afunctional group. This produces molecules which simultaneously containtwo silicon atoms and two functional groups such as carboxyl, amine,hydroxyl or mercapto groups and the like, and these molecules open theway to a variety of polymers such as polyesters, polyamides,polyurethanes, polyimides and the like.

The compounds of the formula (I) are very particularly suitable for thesynthesis of unsaturated disilanes with carbo-functional units, whichform a second subject of the present invention.

B. More particularly, a second subject of the invention resides in thepolyethylenic silicon compounds of the general formula: ##STR31## inwhich R and R', R₁ and R₁ ', n and n', R₂ and R₂ ', and X and X', whichmay be identical or different, have the general and specific meaningsalready given for the formula (I), and

r and r' are identical or different organic radicals having from 1 to 30carbon atoms, chosen from the groups consisting of:

a. divalent radicals --G-- and --G'-- and

b. trivalent radicals --G₁ < and --G₁ '<, G, G', G₁ and G₁ ' having themeanings given to G for formula (I) and

Ψ is an organic radical chosen from the group consisting of: ##STR32##In the formulae V to VIII: β and β' independently represent an oxygen ornitrogen atom,

R" represents a valency bond or a divalent organic radical,

R"' represents a trivalent organic radical,

R"" represents a tetravalent organic radical and

T and T' represent identical or different functional groups chosen fromthe group consisting of: ##STR33##

In the formulae, R₃ has the meaning already given.

More precisely, the various preceding symbols can assume the followingmeanings:

I - Radicals R and R'; R₁ and R₁ '; R₂ and R₂ '; X and X'; G and G'; G₁and G₁ '; n and n':

They can assume all the specific meanings mentioned for R, R₁, R₂, X, Gand n for the formula (I).

II - RADICAL R':

It symbolises more particularly:

1. A saturated or unsaturated, aliphatic, straight or branched, orcycloaliphatic, hydrocarbon radical optionally substituted by one ormore chlorine atoms, or a monocyclic or polycyclic arylene radical ofwhich the rings form, with one another, ortho-condensed or ortho- andperi-condensed systems.

These aromatic radicals can be substituted by halogen atoms; alkylradicals having from 1 to 4 carbon atoms, such as methyl and ethylradicals; alkenyl radicals having from 2 to 4 carbon atoms, preferablyα- or β-ethylenic radicals; or by one or more functional groups such ascyano, ether, urethane, amide, ester (especially methylcarboxy andmethoxycarbonyl), nitro, amino, hydroxyl and hydroxycarbonyl.

2. A saturated, unsaturated or aromatic, monocyclic or polycyclic,heterocyclic radical containing at least one of the hetero-atoms O, Nand S, and optionally substituted by methyl radicals.

3. A divalent radical consisting of a chain of groups as defined inparagraphs 1 and/or 2 and linked to one another by:

a valency bond,

and/or at least one of the following groups: ##STR34## in which formulaeR₇ and R₈ have the meaning already indicated, or an organic radicalcontaining silicon such as ##STR35##

In these formulae, n₂ represents an integer from 1 to 3, and R₁₀ andR₁₁, which may be identical or different, represent an alkyl grouphaving from 1 to 6 carbon atoms, an alkenyl radical having from 2 to 4carbon atoms, preferably an α- or β-ethylenic radical, a phenyl group ora hydrolysable group chosen from the following: ##STR36## wherein R₁₂and R₁₂ ', which may be identical or different, represent alkyl groupshaving from 1 to 3 carbon atoms.

Amongst the radicals which have just been mentioned, R" represents moreparticularly:

a. a straight or branched alkylene, alkylidene, alkenylene oralkenylidene radical having at most 12 carbon atoms, or a cycloalkyleneor cycloalkenylene radical having 5 to 8 carbon atoms in the ring.

By way of illustration, there may be mentioned the methylene, ethylene,ethylidene, cyclohexylene and butylene radicals.

b. A phenylene, tolylene, xylylene and naphthylene radical optionallysubstituted by one or more chlorine atoms, nitrile, amide or ester(especially methylcarbonyloxy and methoxycarbonyl) groups, or alkyloxyradicals having from 1 to 4 carbon atoms, such as the methoxy radical.

c. A saturated, unsaturated or aromatic monocyclic heterocyclic radicalcontaining as the hetero-atom one or more oxygen, nitrogen or sulphuratoms, and containing 4 to 6 (total) atoms in the ring; the heterocyclicradicals can be substituted by one or two methyl groups.

The following radicals may be mentioned by way of illustration:##STR37##

d. A divalent radical consisting of a chain of two to four groups asdefined in paragraphs a and/or b and/or c and linked to one another by avalency bond and/or by at least one of the following groups: --O--,--NH--, --COO--, --CONH--, --SO₂ --, --N═N--, ##STR38## --CO-- and/or byan alkylene or alkylidene group having from 1 to 4 carbon atoms, or byan organic radical containing silicon, such as: ##STR39## (wherein n₂represents an integer from 1 to 3, and R₁₀ and R₁₁ denote a methyl orphenyl radical).

By way of illustration, the radicals of the following formulae may bementioned: ##STR40##

Preferably, R" represents:

an alkylene radical having from 1 to 8 carbon atoms, a cyclohexyleneradical, a phenylene, tolylene or xylylene radical, or a pyridyleneradical, or a divalent radical containing 2 to 4 phenylene groups linkedto one another by a valency bond, by an oxygen atom, by one of thegroups: ##STR41## or by an alkylene or alkylidene group having from 1 to4 carbon atoms, or by an organic radical containing silicon, such as:##STR42## (wherein n₂ represents an integer from 1 to 3 and R₁₀ and R₁₁denote a methyl or phenyl radical), or a divalent radical containing 2alkylene groups having from 1 to 4 carbon atoms linked to a phenylenegroup by a valency bond, by an oxygen atom or by one of the groups:##STR43##

III - RADICALS R"' and R""

R"' and R"" are multivalent radicals which can be:

1. A linear or branched saturated aliphatic hydrocarbon radical havingfrom 2 to 20 carbon atoms.

2. A saturated or unsaturated alicyclic hydrocarbon radical containingfrom 5 to 6 carbon atoms in the ring.

3. A saturated or unsaturated heterocyclic radical containing at leastone of the atoms O, N and S and from 4 to 6 atoms in the ring.

4. A monocyclic or polycyclic aromatic hydrocarbon radical in which therings are fused or are linked to one another by a valency bond or by analkylene or alkylidene radical having from 1 to 4 carbon atoms or by oneof the following groups: ##STR44## in which Δ represents a linear orbranched alkylene radical having fewer than 13 carbon atoms, acycloalkylene radical with 5 or 6 carbon atoms in the ring or amonocyclic or polycyclic arylene radical, and L represents a hydrogenatom, an alkyl radical having from 1 to 4 carbon atoms or a phenylradical. Furthermore, these aromatic radicals can be substituted bymethyl groups and/or chlorine atoms.

More particularly, R"' and R"" represent:

a. a linear or branched saturated aliphatic hydrocarbon radical havingfrom 2 to 10 carbon atoms.

By way of illustration, the following radicals may be mentioned:##STR45##

b. a saturated or unsaturated alicyclic hydrocarbon radical having from5 to 6 carbon atoms in the ring.

These radicals are, for example, the following: ##STR46##

c. a saturated or unsaturated heterocyclic radical containing 5 or 6atoms in the ring and containing at least one of the atoms O, N and S.

By way of illustration, the heterocyclic radicals of the followingformulae may be mentioned: ##STR47##

d. a monocyclic or polycyclic hydrocarbon radical in which the rings arefused or linked to one another by a valency bond or by an alkylene oralkylidene group having from 1 to 4 carbon atoms, such as the methylene,ethylene and isopropylidene radicals, by an oxygen atom or by one of thefollowing groups: ##STR48## By way of illustration, R"' and R"" canrepresent one of the radicals ##STR49##

Preferably, R"' and R"" are trivalent or tetravalent radicals containing1 or 2 benzene nuclei linked to one another by a valency bond, an oxygenatom, a methylene or isopropylidene radical or one of the groups:##STR50##

IX - GROUPS T and T'

T and T' preferably represent one of the following groups: ##STR51##

Amongst these compounds of the formula (IV), the compounds moreparticularly claimed are those for which the various radicals of thesaid formula have the following meanings:

n and n': an integer equal to 1.

R and R': A linear alkenyl group having from 2 to 6 carbon atoms andespecially a vinyl or allyl group.

R₁ and R₁ ': an alkyl radical having from 1 to 5 carbon atoms,optionally substituted by 1 to 4 atoms of chlorine and/or fluorine, or aphenyl radical.

R₂ and R₂ ': a methylene or ethylene group.

X and X': one of the following groups: ##STR52## wherein R₅ represents ahydrogen atom or a methyl or ethyl radical.

βand β': an oxygen atom.

G and G': an alkylene or alkylidene radical having from 1 to 6 carbonatoms, a cyclohexylene radical, a phenylene, tolylene or xylyleneradical, a radical formed by two phenylene groups linked to one anotherby a valency bond, a methylene or isopropylidene groups, an oxygen atomor one of the groups --NH--, --SO₂ --, --CO-- and --CO--NH--.

G₁ and G₁ ': a 1,2,4-benzenetriyl radical or a trivalent radicalcontaining two benzene nuclei linked to one another by a valency bond ora carbonyl, sulphone, methylene or isopropylidene group.

R': an alkylene radical having from 1 to 8 carbon atoms, a cyclohexyleneradical, a phenylene, tolylene or xylylene radical or a pyridyleneradical, a divalent radical containing from 2 to 4 phenylene groupslinked to one another by a valency bond, by an oxygen atom or by one ofthe following groups: ##STR53## or by an alkylene or alkylidene grouphaving from 1 to 4 carbon atoms, or by an organic radical containingsilicon, such as: ##STR54## (wherein n represents an integer from 1 to 3and R₁₀ and R₁₁ denote a methyl or phenyl radical), or a divalentradical containing 2 alkylene groups having from 1 to 4 carbon atomslinked to a phenylene group by a valency bond, by an oxygen atom or byone of the groups: ##STR55##

R"' and R"": trivalent or tetravalent radicals containing 1 or 2 benzenenuclei linked to one another by a valency bond, by an oxygen atom, by amethylene or isopropylidene radical or by one of the groups ##STR56##(wherein R₈ has the meaning given above).

R₃ : denotes a hydrogen atom or a methyl group.

T and T': one of the following groups: ##STR57##

By way of illustration, the following compounds of the formula (IV) maybe mentioned: ##STR58## Obviously, compounds analogous to the compounds(1) to (24), obtained by replacing the vinyl group by an allyl group,could be mentioned.

The compounds of particular interest are those in which the numbers nand n' are identical and the radicals and groups R, R₁, R₂, R₃, X, G,G₁, β and T are respectively identical to R', R'₁, R'₂, R'₃, X', G', G₁', β' and T'.

The compounds preferred are those of the formula (3), (4), (5), (6),(7), (17), (18), (19), (20), (21), (22), (23) and (24).

PREPARATION OF THE POLYETHYLENIC SILICON COMPOUNDS OF THE FORMULA (IV)

The compounds corresponding to the general formula (IV) can be obtainedin accordance with a process which consists of reacting

1. an organo-silicon compound of the general formula (I) correspondingto the formula (A): ##STR59## by itself, or together with anorgano-silicon compound of the formula (A') ##STR60## with

2. a compound hereafter referred to as the coupling agent, of theformula (B)

    t.sub.1 -- .tbd. -- t'.sub.1                               (b)

in the formulae (A) and (A'), n, n', R, R', R₁, R'₁, R₂, R'₂, X, X', Tand T' have the meanings already given for the formulae (I) and (IV). Yand Y', which may be identical or different, represent one of thefollowing functional groups, chosen from amongst those mentioned for Yin connection with the formula (I) ##STR61## wherein R₃ and R₄ have themeanings already given, and T and T' represent:

G and G' if Y and Y' represent the groups (IX) to (XV), and/or

G₁ and G₁ ' if Y and Y' represent the group (XVI).

In the formula (B), .tbd. represents a ##STR62## group or one of theradicals R", R"' and R"", which have the meanings already given for theformulae (VI), (VII) and (VIII).

T₁ and T₁ ', which may be identical or different, represent a chlorineatom or one of the groups defined for Y and Y'.

.tbd. represents a carbonyl group if T₁ and T₁ ' represent a chlorineatom, and a radical R"' or R"" if T₁ and T₁ ' represent one or twoanhydride groups.

More precisely, the compounds of the formula (B) correspond to theformulae ##STR63##

The coupling agent employed in the course of the synthesis of thecompound (IV) can contain two identical or different groups T₁ and T₁ 'which, naturally, should not be reactive towards one another under theconditions of carrying out the synthesis of the compounds of the formula(IV).

The compounds (B₂) and (B₃) are so chosen that the functional groups T₁and/or T₁ ' can react with the groups Y and/or Y' carried by thecompounds (A) and/or (A').

Preferably, identical groups T₁ and T₁ ' are chosen if a coupling agentcorresponding to the formula (B₂) is employed.

If two compounds (A) and (A') which differ in respect of their group Yand Y' are reacted with the compound (B), they must be chosen as toavoid any condensation between them under the conditions of thereaction.

The choice of the groups T₁, T₁ ', Y and Y' can easily be decided bythose skilled in the art on the basis of the nature of the siliconcompounds and of the coupling agent.

By way of example, the synthesis of the compounds of the formula (IV)can be illustrated by the following reaction schemes: ##STR64##

Thus T and T' and β and β' previously defined result from the reactionbetween the groups Y, Y' and T₁, T₄ '.

The amounts of reactants to be employed depend on the nature of thereactants brought together; they can be close to the stoichiometricamount or, without disadvantage they can differ therefrom.

In general, at least two mols of compound A (or 1 mol of each compound Aand A') and reacted with one mol of compound B.

The condensation reactions of the organo-silicon compound or compoundsand of the compound (B) are carried out in accordance with the generalprocesses described in the literature and well known to those skilled inthe art.

The organo-silicon compounds of the formula (IV) in which T and T'represent an amide group are obtained by condensation of a compoundwhich carries an acid chloride group and a diamine compound. Thereaction is, as a general rule, carried out at a temperature of from-20° to 200° C and preferably -10° to 100° C. One of the reactants isgradually introduced into the reaction medium containing the otherreactant. In general, the reaction is carried out in a medium which isan adequate solvent, consisting, for example, of acetone,dimethylacetamide, carbon tetrachloride or their mixtures, in thepresence of the usual acceptors of hydrochloric acid. When the reactionhas been completed, the compounds (IV) can be isolated from the reactionmedium by any known means.

It is also possible to carry out this type of condensation at theinterface of two immiscible solvents each containing one of thereactants and the acid acceptor [see N.O.V. SONNTAG - Chem. Rev. 52,268-294 (1953), J. ZABICKY -- The Chemistry of Amides (1970), p. 73(Interscience Publishers)].

The organo-silicon compounds of the formula (IV) in which T and T' areester groups can be prepared either directly by reaction of a compoundhaving a free carboxylic acid group with a compound having a hydroxylgroup, or by trans-esterification in the presence of the usualcatalysts. In this latter case, the methyl ester of the acid compound ispreferably used. It is also possible to obtain these compounds (IV) byreaction of the acid anhydrides or acid halides with the correspondinghydroxylic compounds, if appropriate in the presence of an acceptor forthe hydracid [see KIRK-OTHMER, Encyclopaedia of Chemical Technology -2nd edition, 8, 313 to 339, and N.O.V. SONNTAG - Chem. Rev. 52, 312-321(1953)].

The organo-silicon compounds (IV) with imide groups can be obtained in amanner which is in itself known by heating an acid anhydride with acompound having a primary amine group so as to give the correspondingimide directly. According to another method which is also known, it ispossible to form, as an intermediate stage, the ammonium saltcorresponding to the diacid and to the amine, in accordance with theusual methods, and then bring about the cyclisation by heating the salt,with elimination of water. It is also possible to form, as anintermediate, an acid amide which is subsequently dehydrated by heating.

In all cases, the temperature will be chosen in accordance with thereactants employed.

In general, this temperature is from 50 to 200° C. The formation of theimides can be carried out in organic solvents or diluents which areinert towards the reactants.

The organo-silicon compounds (IV) with urea or urethane groups areeasily obtained from reactants containing, firstly, isocyanate groups,and, secondly, amine or hydroxyl groups, the reaction being carried outunder the usual conditions for the reaction of isocyanates withcompounds containing active hydrogen (see KIRK-OTHMER - Encyclopaedia ofChemical Technology, 2nd edition, 21, 63 to 74). In general, thereaction temperature, which can be varied in accordance with thecompound, containing active hydrogen, which is employed, is from 0° to100° C and more particularly from 0° to 50° C. The condensation can becarried out in the presence of the usual catalysts (e.g. tertiaryamines, metal halides, aluminium chloride, tin chloride, organo-siliconcompounds and the like). The reaction can be carried out in bulk orpreferably in suspension or in solution in a solvent which is inerttowards the reactants, especially towards isocyanates. For example,aliphatic, cycloaliphatic or aromatic hydrocarbons or their chlorinatedderivatives, or ethers, can be employed for this purpose.

REACTANTS EMPLOYED cl I - NATURE OF THE COUPLING AGENT

By way of illustration, the following compounds, which have twoidentical or different functional groups, may be mentioned amongst thecoupling agents (B):

1. corresponding to the formula B₁

phosgene

2. corresponding to the formula B₂

a. dicarboxylic acids and their derivatives (esters and acid chlorides)

As examples of dicarboxylic acids there may in particular be mentioned:

Aliphatic acids such as oxalic acid, malonic acid, succinic acid,glutaric acid, adipic acid, 2,4-dimethyladipic acid, pimelic acid,suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, fumaricacid, maleic acid, methyliminodiacetic acid and3-dimethylamino-hexanedioic acid.

Cycloalkanedicarboxylic acids such as 1,4-cyclohexanedicarboxylic acidand 3-dimethylamino-1,2-cyclopentanedicarboxylic acid.

Aromatic diacids such as phthalic acid, isophthalic acid, terephthalicacid, phenylenediacetic acid, 1,5-naphthalenedicarboxylic acid,1,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid,3,3'-diphenyldicarboxylic acid, bis-(4-hydroxycarbonyl)-phenyl ether,bis-(3-hydroxycarbonyl)-phenyl ether,4,4'-dihydroxycarbonyl-diphenylsulphone and3,3'-dihydroxycarbonyl-diphenylsulphone.

Pyrimidine-dicarboxylic acids or imidazole-dicarboxylic acids.

It is also possible to use, as the coupling agent, the acid chloridesand the esters, preferably the methyl esters, obtained from thesedicarboyxlic acid compounds.

The diacids used preferentially are the following: oxalic acid, succinicacid, adipic acid, fumaric acid, isophthalic acid, terephthalic acid,1,5-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid and3,3'-diphenyldicarboxylic acid.

b. The primary and secondary diamines

Hexamethylenediamine, octamethylenediamine, decamethylenediamine,2,5-dimethyl-heptamethylenediamine, bishexamethylenetriamine,diethylenetriamine, tetraethylenepentamine,bis-(4-aminocyclohexyl)-methane, 2,2-bis-(4-aminocyclohexyl)-propane,1,4-diaminocyclohexane, m-phenylenediamine, p-phenylenediamine,m-xylenediamine, p-xylylenediamine, benzidine,bis-(4-aminophenyl)-methane, 2,2-bis-(4-aminophenyl)-propane,4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulphide,4,4'-diaminodiphenylsulphone, 4,4'-diaminobenzophenone,4,4'-diaminobenzanilide, 4,4'-diamino(phenyl benzoate),3,3'-dicarboxy-benzidine, 1,1-bis-(p-aminophenyl)-phthalane,4,4'-N,N'-bis-(p-aminobenzoyl)-diamino-diphenylmethane,bis-p-(4-amino-phenoxycarbonyl)-benzene, bis-p-(4-aminophenoxy)-benzene,1,5-diaminonaphthalene, 2,6-diaminopyridine,6,6'-diamino-2,2'-dipyridyl, 2,5-bis-(m-aminophenyl)-1,3,4-oxadiazole,2,5-bis-(p-aminophenyl)-1,3,4-oxadiazole,2,5-bis-(m-aminophenyl)-thiazolo(4,5d)thiazole,5,5'-di-(m-aminophenyl)-(2,2')-bis-(1,3,4-oxadiazolyl),4,4-bis-(p-amino-phenyl)-2,2'-dithiazole,m-bis-[4-(p-aminophenyl)-2-thiazolyl]-benzene,2,2'-bis(m-aminophenyl)-(5,5')-dibenzimidazole,3,5-diamino-1,2,4-triazole, 3,5-bis-(4-aminophenyl)-pyridine,bis-(4-aminophenyl)-methylphosphine oxide,bis-(4-aminophenyl)-phenylphosphine oxide,N,N'-bis-(4-aminophenyl)-methylamine, bis-(4-methylaminophenyl)-methane,bis-(4-methylaminophenyl) ether, 2,2-bis-(4-methylaminophenyl)-propane,bis-(3-methylaminophenyl)-sulphone, 1,3-bis-methylaminobenzene,bis-(4-methylaminocyclohexyl)-methane, N,N'-diethylhexamethylenediamine,2,5-bis-methylamino-1,3,4-oxadizole, 1,2-bis-(3-methylaminopropoxy)-ethane, (4-methylaminophenyl)(4'-aminophenyl)-methane, 4-methylaminobenzene 4'-aminobenzene ether,4-methylaminophenyl 4'-aminophenyl sulphone,1-methylamino-4-amino-benzene, 2-methylamino-4-amino-toluene,2-methylamino-5-amino-anisole, 3-methylamino-propylamine,2-ethoxy-4-methylamino-aniline, 3'-methylamino-4-benzoylaminoaniline,3-ethylaminoethoxy-propylamine, 3-ethylaminoethylmercapto-propylamine,6-methylamino-hexylamine, (4-methylaminocyclohexyl)(4'-aminocyclohexyl)-methane,2-p-methylaminophenyl-5-amino-1,3,4-oxadiazole,2-m-methylaminophenyl-5-amino-benzoxazole,1,3-bis-(3-p-aminophenoxypropyl)-tetramethyldisiloxane,1,3-bis-(2-p-aminophenoxyethyl)-tetramethyldisiloxane,1,2-bis-(2-p-aminophenoxyethyl-dimethylsilyl)-ethane and4,4'-diamino-azobenzene.

The diamines used preferentially are the following:

Hexamethylenediamine, 2,2-bis-(4-aminocyclohexyl)-propane,m-phenylenediamine, p-phenylenediamine, m-xylenediamine,p-xylenediamine, bis-(4-aminophenyl)-methane, 4,4'-diaminodiphenylether, 4,4'-diaminobenzophenone, 4,4'-diamino(phenyl benzoate),4,4'-N,N'-bis-(p-aminobenzoyl)-diaminodiphenylmethane,bis-p-(4-aminophenoxy)-benzene, 2,6-diaminopyridine,2,5-bis-(p-aminophenyl)-1,3,4-oxadiazole,4,4'-bis-(p-aminophenyl)-2,2'-dithiazole, 3,5-diamino-1,2,4-triazole,1,3-bis-(4-aminophenyl)-methylphosphine oxide,1,3-bis-(2-p-aminophenoxyethyl)-tetramethyldisiloxane and1,2-bis-(2-p-aminophenoxyethyl-dimethylsilyl)-ethane.

c. Diisocyanates

1,2-Diisocyanato-propane, 1,2-diisocyanato-butane,1,3-diisocyanato-butane, 1,6-diisocyanato-hexane,1,3-diisocyanato-benzene, 1,4-diisocyanato-benzene,2,4-diisocyanato-toluene, 2,6-diisocyanato-toluene,2,4-diisocyanatoxylene, 2,6-diisocyanato-xylene,3,3'-diisocyanato-diphenyl, 4,4'-diisocyanato-diphenyl,3,3'-diisocyanato-diphenylmethane, 4,4'-diisocyanato-diphenylmethane,4,4'-diisocyanato-3,3'-dimethyl-diphenyl,4,4'-diisocyanato-3,3'-dimethyl-diphenylmethane,4,4'-diisocyanato-diphenylethane, 3,3'-diisocyanatodiphenyl ether,4,4'-diisocyanato-diphenyl ether, 3,3'-diisocyanato-diphenylsulphone,4,4'-diisocyanato-diphenylsulphone, 3,3'-diisocyanato-benzophenone,4,4'-diisocyanato-benzophenone, 3,3'-diisocyanato-dicyclohexylmethane,4,4'-diisocyanatodicyclohexylethane, 1,5-diisocyanato-napthalene,4,4'-diisocyanato-3,3'-dichloro-diphenyl and4,4'-diisocyanato-3,3'-dimethoxy-diphenyl.

The diisocyanates used preferentially are the following:

1,6-Diisocyanato-hexane, 2,4-diisocyanato-toluene,2,6-diisocyanato-toluene, 2,4-diisocyanato-xylene,4,4'-diisocyanato-diphenyl, 4,4'-diisocyanato-diphenylmethane,4,4'-diisocyanato-diphenyl ether, 4,4'-diisocyanato-diphenylsulphone,4,4'-diisocyanato-benzophenone, 4,4'-diisocyanato-dicyclohexylethane and1,5-diisocyanato-naphthalene.

d. Diols and diphenols

Ethylene glycol, diethylene glycol, triethylene glycol, tetraethyleneglycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol,1,3-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol,1,6-hexanediol, 1,7-heptanediol, 2,2-dimethyl-1,3-propanediol,1,8-octanediol, 1,12-dodecanediol, 3,13-tetradecanediol,2-ethyl-1,8-octanediol, 3-ethyl-1,10-decanediol,3,6-diethyl-1,8-octanediol, 4,7-diethyl-2,9-decanediol,2-butene-1,4-diol, 2-pentane-1,5-diol, 2-heptene-1,7-diol,2-butine-1,4-diol, 1,4-cyclohexanediol, N-phenyldiethanolamine,2,2'-sulphonyl-diethanol, 4,4'-sulphonyldibutanol,3,3'-[sulphonyl-bis-(3-propyl-sulphonyl)]-dipropanol,2,2'-(p-phenylenedioxy)-diethanol, 3,3'-(p-xylylenedioxy)-dipropanol,4,4'-(p-phenylenedisulphonyl)-dibutanol,6,6'-(p-xylylenedisulphonyl)-dihexanol,2,2'-(4,4'-diphenylenedioxy)-diethanol,1,4-bis-(β-hydroxyethyl)-cyclohexane,1,4-bis-(δ-hydroxybutyl)-cyclohexane, 4,4'-bis(hydroxymethyl)-diphenyl,2,6-bis-(hydroxymethyl)-naphthalene,1,5-bis-(β-hydroxyethyl)-naphthalene, 1,4-bis-(β-hydroxyethyl)-benzene,1,4-bis-(γ-hydroxypropyl)-benzene, 2-(β-hydroxyethyl)-benzyl alcohol,ethylene glycol terephthalate, hydroquinone, resorcinol, catechol,p-xylene glycol, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene,4,4'-dihydroxydiphenyl, bis-(4-hydroxyphenyl)-methane,bis-(4-hydroxyphenyl)-methylphenylmethane,bis-(4-hydroxyphenyl)-sulphone, 2,2-bis-(4-hydroxyphenyl)-propane andthe bis-(4-hydroxyphenyl)-tolylmethanes.

The diols and diphenols used preferentially are the following:

Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol,1,6-hexanediol, 1,7-heptanediol,4,4'-(p-phenylenedisulphonyl)-dibutanol,1,4-bis-(δ-hydroxybutyl)-cyclohexane, 1,4-bis-(β-hydroxyethyl)-benzene,hydroquinone, resorcinol, 1,5-dihydroxynaphthalene,4,4'-dihydroxydiphenyl, bis-(4-hydroxyphenyl)-methan andbis-(4-hydroxyphenyl)-sulphone.

d. Dithiols

1,2-Ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol,1,6-hexanedithiol, 2-butene-1,4-dithiol, 3-hexyne-1,6-dithiol,p-phenylenedithiol, 1,4-bis-(α-mercaptomethyl)-benzene,1,4-bis-(β-mercaptoethyl)-benzene, 1,4-bis-(γ-mercaptoethyl)-benzene and1,5-dimercaptonaphthalene.

The dithiols used preferentially are the following:

1,6-Hexanedithiol, p-phenylenedithiol and 1,5-dimercaptonaphthalene.

e. Coupling agents with different functional groups

6-Hydroxy-caproic acid, 10-hydroxy-decanoic acid, 12-hydroxy-stearicacid, 6-amino-caproic acid, 9-amino-nonanoic acid, 11-amino-undecanoicacid, 12-amino-stearic acid, ethanolamine, 3-amino-propanol,4-amino-butanol, 5-amino-pentanol, 6-amino-hexanol,6-amino-5-methyl-1-hexanol, 10-amino-decanol,4-p-aminophenyl-cyclohexanol, p-hydroxymethylbenzylamine,4-hydroxymethyl-4'-aminomethyl-diphenyl, p-aminophenylethyl alcohol,N-β-aminoethyl-N-ω-hydroxyhexyl-aniline, 4-amino-thiophenol andmonothioethylene glycol.

The compounds used preferentially are the following:

6-Hydroxy-caproic acid, 6-amino-caproic acid, ethanolamine and4-p-aminophenyl-cyclohexanol.

3. To the formula B₃

By way of illustration, the compounds containing an anhydride group andan acid group may be mentioned:

Trimellitic anhydride, the 2:3 anhydride of2,3,6-naphthalenetricarboxylic acid, the 1:2 anhydride of1,2,5-naphthalenetricarboxylic acid, the 3:4 anhydride of3,4,4'-diphenyltricarboxylic acid, the 3:4 anhydride of3,4,3'-diphenylsulphonetricarboxylic acid, the 3:4 anhydride of3,4,4'-diphenyl ether tricarboxylic acid, the 1:2 anhydride of1,2,4-cyclopentadienetricarboxylic acid and the 3:4 anhydride of3,4,4'-benzophenonetricarboxylic acid.

The compounds used preferentially are the following:

Trimellitic anhydride, the 1:2 anhydride of1,2,5-naphthalenetricarboxylic acid, the 3:4 anhydride of3,4,3'-diphenylsulphonetricarboxylic acid, the 3:4 anhydride of3,4,4'-diphenyl ether tricarboxylic acid and the 3:4 anhyride of3,4,4'-benzophenonetricarboxylic acid.

4. To the formula B₄

Amongst the dianhydrides which can be used there may be mentioned, byway of example, the following dianhydrides:

Ethylenetetracarboxylic dianhydride, methanetetracarboxylic dianhydride,1:2, 3:4-butanetetracarboxylic dianhydride, 1:2,4:5-pentanetetracarboxylic dianhydride, pyromellitic dianhydride, 1:6,2:3-benzenetetracarboxylic dianhydride, 2:3,2':3'-diphenyltetracarboxylic dianhydride, 3:4,3':4'-diphenyltetracarboxylic dianhydride, 3:4,3':4'-diphenylmethanetetracarboxylic dianhydride, 3:4,3':4'-(2,2-diphenyl)-propanetetracarboxylic dianhydride, 3:4,3'4'-diphenylsulphonetetracarboxylic dianhydride, 3:4, 3':4'-diphenylether tetracarboxylic dianhydride, 3:4,3':4'-benzophenonetetracarboxylic dianhydride, 2:3,6:7-naphthalenetetracarboxylic dianhydride, 1:2,5:6-naphthalenetetracarboxylic dianhydride, 1:2,4:5-naphthalenetetracarboxylic dianhydride, 1:8,4:5-naphthalenetetracarboxylic dianhydride, 1:8,4:5-decahydronaphthalenetetracarboxylic dianhydride, 1:2,5:6-(4,8-dimethyl)-1,2,3,5,6,7-hexahydronaphthalenetetracarboxylicdianhydride, 1:8, 4:5-(2,6-dichloro)-naphthalenetetracarboxylicdianhydride, 1:8, 4:5-(2,7-dichloro)-naphthalenetetracarboxylicdianhydride, 1:8, 4:5-(2,3,6,7-tetrachloro)-naphthalenetetracarboxylicdianhydride, 1:10, 8:9-phenanthrenetetracarboxylic dianhydride, 3:4,9:10-perylenetetracarboxylic dianhydride, 1:2,3:4-cyclopentanetetracarboxylic dianhydride, 1:2,4:5-cyclohexanetetracarboxylic dianhydride, 2:3,4:5-pyrrolidinetetracarboxylic dianhydride, 2:3,5:6-pyrazinetetracarboxylic dianhydride, 2:3,4:5-thiophenetetracarboxylic dianhydride,cyclopentadienyltetracarboxylic dianhydride, 3:4,3':4'-azoxybenzenetetracarboxylic dianhydride and 3:4,3':4'-azobenzenetetracarboxylic dianhydride.

The dianhydrides used preferentially are the following:

Ethylenetetracarboxylic dianhydride, pyromellitic dianhydride, 2:3,2':3'-diphenyltetracarboxylic dianhydride, 3:4,3':4'-(2,2-diphenyl)-propanetetracarboxylic dianhydride, 3:4,3':4'-diphenylsulphonetetracarboxylic dianhydride, 3:4, 3':4'-diphenylether tetracarboxylic dianhydride, 3:4,3':4'-benzophenonetetracarboxylic dianhydride, 2:3,6:7-naphthalenetetracarboxylic dianhydride and 1:2,3:4-cyclopentanetetracarboxylic dianhydride.

II - NATURE OF THE ORGANO-SILICON COMPOUNDS (A) AND (A')

By way of illustration, the following compounds may be mentioned:

1-Amino-4-(vinyldimethylsilylmethoxy)-benzene,1-hydroxy-4-(vinyldimethylsilylmethoxy)-benzene,1-mercapto-4-(vinyldimethylsilylmethoxy)-benzene,1-carboxy-4-(vinyldimethylsilylmethoxy)-benzene,4-(vinyldimethylsilylmethoxy)-benzoic acid chloride,1-methoxycarbonyl-4-(vinyldimethylsilylmethoxy)-benzene,1-isocyanato-4-(vinyldimethylsilylmethoxy)-benzene,1-amino-4-(2-vinyldimethylsilyl-ethoxy)-benzene,1-hydroxy-4-(2-vinyldimethylsilyl-ethoxy)-benzene,1-amino-4-(3-vinyldimethylsilyl-propoxy)-benzene,1-mercapto-4-(3-vinyldimethylsilyl-propoxy)-benzene,1-amino-4-(vinyldimethylsilylmethoxycarbonyl)-benzene,1-carboxy-4-(vinyldimethylsilylmethoxycarbonyl)-benzene,1-amino-4-(vinyldimethylsilylmethylthio)-benzene,1-ethoxycarbonyl-4-(vinyldimethylsilylmethylthio)-benzene,1-ethoxycarbonyl-4-(vinyldimethylsilylmethylthiocarbonyl)-benzene,1-ethoxycarbonyl-4-(vinyldimethylsilylmethylthio-thiocarbonyl)-benzene,4-vinyldimethylsilylmethoxy-4'-amino-diphenylmethane,4-vinyldimethylsilylmethoxy-4'-chlorocarbonyl-diphenylmethane,4-vinyldimethylsilylmethoxy-4'-amino-diphenyl ether,4-vinyldimethylsilylmethoxy-4'-methoxycarbonyl-diphenyl ether,4-vinyldimethylsilylmethoxy-4'-amino-diphenylsulphone,4-vinyldimethylsilylmethoxy-4'-amino-diphenyl,4-vinyldimethylsilylmethoxy-4'-hydroxy-diphenyl,4-vinyldimethylsilylmethoxy-4'-chlorocarbonyl-diphenyl,1-amino-4-(allyldimethylsilylmethoxy)-benzene,1-amino-4-(but-1-enyl-dimethylsilylmethoxy)-benzene,1-amino-4-(methyldivinylsilylmethoxy)-benzene,1-amino-[(1,2,2-trichlorovinyl)-dimethylsilylmethoxy]-benzene,1-amino-4-(vinyldiphenylsilylmethoxy)-benzene,1-amino-4-[vinyl-bis(3,4-dichlorophenyl)-silylmethoxy]-benzene,1-amino-4-(methylphenylvinylsilylmethoxy)-benzene,1-amino-4-(methyl-γ-cyanopropylvinylsilylmethoxy)-benzene,N-p-aminophenyl-N-vinyldimethylsilylmethyl-methylamine,N-p-ethoxycarbonylphenyl-N-vinyldimethylsilylmethyl-methylamine, andethyl ester of 4-(vinyldimethylsilylmethoxy)-butanoic acid,4-vinyldimethylsilylmethoxy-butylamine,3-amino-5-(vinyldimethylsilylmethoxy)-pyridine,3-ethoxycarbonyl-5-(vinyldimethylsilylmethoxy)-pyridine,1-amino-4-[(dimethylvinylsiloxy)-dimethylsilylmethoxy]-benzene,1-aminomethyl-4-(vinyldimethylsilylmethoxy-)benzene,1-hydroxymethyl-4-(vinyldimethylsilylmethoxy-)benzene, the ethyl esterof 2-(vinyldimethylsilylmethyl)-thioglycolic acid,1-amino-4-(methyl-γ-trifluoropropylvinylsilylmethoxy)-benzene and4-vinyldimethylsilylmethoxy)-phthalic anhydride.

The unsaturated organo-silicon compounds of the formula (IV) areproducts which are particularly interesting because of the specialreactivity conferred on them by the presence of the ethylenic doublebonds, especially towards organo-silicon compounds containinghydrogenosilane groups. This property can be used advantageously -- andthis constitutes a further subject of the present invention -- to obtainpolymers containing fragments of organo-silicon chains and fragments ofcarbo-functional chains.

C. More particularly, a third subject of the present invention residesin thermoplastic polysiloxane elastomers containing carbo-functionalunits, obtained from the compounds of the formula (IV) in which n and n'are equal to 1.

The silicone rubbers have acquired considerable industrial importancebecause of their original chemical, physical and mechanical propertiesand especially because of their behaviour towards cold and heat. Theseelastomers are obtained, by a long and delicate process, fromelastomeric siloxane gums which are themselves in the form of more orless viscous products devoid of valuable mechanical properties. Thesegums are prepared by polymerisation of cyclic siloxane oligomers or bypolycondensation or copolycondensation of siloxane oligomers withterminal functional groups (for example alkoxy, hydroxyl and/orchlorine). The production of the silicone rubbers from polysiloxane gumsrequires firstly the preparation of masterbatches by incorporating intothe gum various ingredients such as fillers (and especially silica in agreat variety of forms), pigments and vulcanising agents, followed bythe vulcanisation of these masterbatches, for example by heating in thepresence of organic peroxides or, in the case of polysiloxane gums withterminal functional groups, by a cold treatment using polyfunctionalcrosslinking agents (silicates, trialkoxysilanes, triacetoxysilanes andthe like). Regardless of the process employed, the vulcanisation, whichmakes it possible to convert a gum devoid of valuable mechanicalproperties to a rubber, must be preceded by the moulding of the desiredobjects because the vulcanised product is devoid of anythermoplasticity. On the other hand, the incorporation of fillers intothe polysiloxane gums has proved indispensable; in effect, the siliconerubbers obtained by vulcanisation of unfilled gums have such lowmechanical properties that they have not found any practical use. Incertain cases the introduction of the fillers into the polysiloxane gumscan have the effect of forming a mixture which is difficult to handleduring the moulding process because of an interaction between the fillerand the gum; it is then necessary to overcome this disadvantage byincorporating ingredients intended to minimise this interaction or torestore sufficient plasticity to the masterbatch. All these operationscomplicate the process of obtaining silicone rubbers and have provedcostly from an economic point of view.

Attempts have been made to avoid the disadvantages referred to abovewhilst preserving the remarkable properties of silicone rubbers, byproceeding to develop thermoplastic elastomeric polymers. The methodgenerally used to arrive at this objective consists of combiningpolysiloxane units and units of organic polycondensates in one polymericchain. Thus it has been proposed, in U.S. Pat. No. 3,189,662, to obtainblock copolycondensates containing polydiorganosiloxane units and unitsof polycarbonates of aromatic diols by reaction of anα-ω-dihalogenopolysiloxane with a diphenol in the presence of a halogenacceptor, to form an intermediate condensate which is then treated withphosgene. Although the polycondensate thus obtained is elastic, it hasthe disadvantage of containing, in its chain, Si--O--C bonds of which itis known that they are less stable to hydrolysis than the silicon-carbonbonds. It has also been proposed to prepare polymers containingpolydiorganosiloxane units linked to one another by purely organic unitsvia intermediate silicon-carbon bonds. Thus it has been proposed, inU.S. Pat. No. 3,176,034, to prepare copolymers containing a plurality ofpolydiorganosiloxane blocks linked to one another by organic units ofthe formula: ##STR65## in which X is a halogen or hydrogen atom or amethyl radical, Y is an alkylene radical and a is 0 or 1, by reaction ofan α,ω-dihydrogenopolydiorganosiloxane with allyl diethers of bisphenolsin the presence of the usual hydrosilylation catalysts. The polymersthus obtained are "thermoplastic fluids" which must be converted bycrosslinking when they are used. Ultimately it is found that nosatisfactory solution has been provided to the problem of obtainingelastomeric thermoplastic polymers which simultaneously have theremarkable properties of silicone rubbers and excellent stability tohydrolysis. The subject of the invention resides precisely in thesolution of this problem.

More precisely, the present invention provides polysiloxanethermoplastic elastomers, characterised in that they exhibit a pluralityof recurring units of the general formula: ##STR66## in which thevarious symbols have the following meaning:

R₁ and R'₁, R₂ and R'₂ and X and X' have the general or specificmeanings given for the formula (I).

Γ and Γ' and Ψ have the general meanings given for the formula (IV).

R₀ and R'₀, which may be identical or different, represent divalentorganic radicals containing from 2 to 10 carbon atoms.

λ and λ', which may be identical or different, denote a valency bond orone of the following organo-silicon groups: ##STR67## wherein R₆ and n₁have the meaning already indicated.

Q₁ to Q₆, which may be identical or different, are defined under R₁.

n₃ is a number ranging from 0 to 2,000.

More precisely, the various symbols shown in the formula (XVII) canassume the following particular meanings:

I - Radicals R₁ and R'₁ ; R₂ and R'₂ ; X and X'; T and T'

These can have all the specific meanings already mentioned for theformulae (I) and (IV).

II - Radicals G and G' and G₁ and G'₁

They can assume the more specific meanings given for the formulae (I)and (IV), with the restriction that if they are aliphatic orcycloaliphatic in nature, G and G' and G₁ and G'₁ do not contain doubleor triple carbon-carbon bonds.

III - Radical R"

It can assume the specific meanings given for the formula (IV) with therestriction that if R" is aliphatic or cycloaliphatic in nature, it doesnot contain double or triple carbon-carbon bonds, and if it representsan aromatic radical it does not contain an alkenyl substituent. In thesame way, the radicals R₁₀ and R₁₁ defined in connection with R"represent only alkyl or phenyl radicals in the case of the compounds ofthe formula (XVII).

IV - Radicals R"' and R""

They can assume the more specific meanings given for the formula IVexcept those which imply the presence of an ethylenic double bond.

V - Radicals R₀ and R'₀

These radicals represent a linear or branched alkylene group optionallysubstituted by 1 to 4 halogen atoms, especially chlorine and/orfluorine, or a cycloalkylene group optionally substituted by 1 to 4atoms of halogen, especially of chlorine and/or fluorine.

More specifically, R₀ and R'₀ symbolise the following groups: ethylene;1,3-propylene; 1,2-propylene; 1,4-butylene; 1,3-butylene; 2,3-butylene;1,5-pentylene; 1,4-pentylene; hexamethylene; octamethylene;decamethylene; monochloroethylene; dichloroethylene;1,2-difluoroethylene; 1,4-cyclohexylene; 1,3-cyclohexylene.

Preferably, R₀ and R'₀ represent linear alkylene groups containing from2 to 6 carbon atoms.

VI - Radicals Q₁ to Q₆

They can preferably assume the specific meanings already mentioned forR₁.

VII - n₃ is preferably from 3 to 500.

Amongst the compounds of the formula (XVII), we claim more specificallythose for which the various radicals of the said formula have thefollowing meanings:

R₀ = R'₀ is a linear alkylene radical having from 2 to 6 carbon atoms.

λ = λ' is a valency bond.

R₁ = R'₁ is an alkyl radical having from 1 to 6 carbon atoms optionallysubstituted by 1 to 4 atoms of chlorine and/or fluorine, or a phenyl,tolyl or xylyl radical optionally substituted by 1 to 4 atoms ofchlorine and/or fluorine.

Q₁ to Q₆, which may be identical or different, have the same meaning asR₁.

R₂ = R'₂ is a methylene or ethylene radical.

X = X' is an oxygen or sulphur atom or one of the radicals ##STR68##wherein R₅ is hydrogen or a methyl or ethyl group.

G = G' is an alkylene or alkylidene radical having from 1 to 6 carbonatoms; a cyclohexylene radical; a phenylene, tolylene, xylylene orbenzylene radical; a radical formed by two phenylene groups linked toone another by a valency bond or by an alkylene or alkylidene grouphaving from 1 to 4 carbon atoms; an oxygen atom; or one of the groups##STR69##

G₁ = G'₁ is a 1,2,4-benzenetriyl radical or one of the followingradicals: ##STR70##

R" represents an alkylene radical having from 1 to 8 carbon atoms; acyclohexylene radical; a phenylene radical; a tolylene radical; axylylene radical; or a divalent radical containing 2 to 4 phenylenegroups linked to one another by a valency bond, by an oxygen atom or thegroups ##STR71## or by an alkylene or alkylidene group containing from 1to 4 carbon atoms; a divalent radical containing 2 alkylene groupshaving from 1 to 4 carbon atoms linked to a phenylene group by a valencybond, by an oxygen atom or by one of the groups ##STR72##

R"' and R"" represent trivalent or tetravalent radicals containing 1 to2 benzene nuclei linked to one another by a valency bond, an oxygen atomor a methylene radical; an isopropylidene radical; or one of the groups##STR73##

n₃ is from 10 to 200 and more particularly from 10 to 80.

T and T' represent one of the groups ##STR74##

β = β' is an oxygen atom.

As specific examples of compounds of the formula (XVII) there may bementioned those which contain a plurality of recurring units of theformulae: ##STR75##

Preparation of the thermoplastic elastomers with recurring units of theformula (XVII)

The thermoplastic elastomers according to the invention can easily beobtained by reaction of at least one diethylenic silicon compound of thegeneral formula: ##STR76## in which R, R', λ, R₁, R₂, X, Γ, Ψ, Γ', X',R'₂, R'₁ and λ' have the meaning given above with the restriction that Rand R' are only ethylenic hydrocarbon radicals with from 2 to 10 carbonatoms, with at least one α,ω-dihydrogenosiloxane of the general formula##STR77## optionally in the presence of customary catalysts for thereaction of compounds having .tbd. Si--H groups with ethylenic doublebonds. By way of example, this polyaddition reaction, which willhereafter be referred to as "hydrosilylation" can be illustrated by thefollowing scheme if R and R' represent a vinyl group and λ and λ'represent a valency bond in the formula (XVIII): ##STR78##

Conditions of the polyaddition reaction

The reaction of the compound (XVIII) with the compound (XIX) is carriedout under the conditions usually employed during the addition ofcompounds having .tbd. Si--H groups with ethylenic compounds, cf. W.NOLL, Chemistry and Technology of Silicones (1968), pages 49 et seq.

Thus, the hydrosilylation reaction can be carried out by heating thereactants at, for example, 150 to 350° C. under autogenic pressure inthe absence of catalysts. It can also be carried out in the presence ofthe customary catalysts, which makes it possible to use less hightemperatures, of the order of 0° to 200° C, and allows the reaction totake place more rapidly under normal pressure.

As catalysts, compounds which generate free radicals are are suitablyused, such as peroxidic compounds (for example acyl peroxides, alkylperoxides and per-esters) or azo compounds. As illustrations of thesecompounds there may be mentioned benzoyl peroxide, acetyl peroxide,lauroyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butylperoxide and N,N'-azo-bis-isobutyronitrile. The same effect is achievedif the process is carried out under ultraviolet irradiation instead ofcarrying out the reaction in the presence of catalysts which generatefree radicals.

Another group of catalysts which can be employed to prepare thethermoplastic elastomers of the invention consists of the metals ofgroup VIII of the periodic classification of the elements (cf. Handbookof Chemistry and Physics, 53rd edition) and their inorganic or organicderivatives. Amongst these metals there may in particular be mentionedPt, Ru, Rh, Pd and Ir. The noble metals are particularly suitable, andplatinum is very specially suitable. They can be used in the form of theelement or in the form of salts or inorganic acids, in particularhalides, salts of organic acids or complexes. Such catalysts have beendescribed in the literature, cf., for example: U.S. Pat. Nos. 2,637,738and 2,632,013; J. L. SPEIER et al., J. Am. Chem. Soc. 79, page 974 etseq. (1957); A. J. CHALK et al., J. Am. Chem. Soc. 87, 16 (1965).

Amongst these catalysts based on metals of group VIII, those based onplatinum are very particularly suitable and are employed preferentially.They can assume various forms which are well-known in the technicalliterature. Thus, it is possible to use the various catalysts based onfinely divided elementary platinum which may or may not be deposited onvarious supports such as carbon black, alumina and silica; catalysts ofthis type have in particular been described in U.S. Pat. No. 2,970,150.Another family of platinum catalysts consists of chloroplatinic acid(cf. U.S. Pat. No. 2,823,218) and the compounds derived therefrom, suchas alkali metal chloroplatinates (cf. J. L. SPEIER, loc. cit.); andcompounds obtained by reaction of chloroplatinic acid with alcohols,ethers or aldehydes (cf. U.S. Pat. No. 3,220,972), with olefines (cf.U.S. Pat. No. 3,159,601) or with cyclopropane (cf. U.S. Pat. No.3,159,662). It is also possible to use the complexes of platinum halideswith compounds which are donors of electron pairs, such as thephosphines, for example bis-(tributylphosphino)-dichloroplatinum (II)and bis-(triphenylphosphino)-dichloroplatinum (II) (cf. A. J. CHALK etal., loc. cit.). Elementary platinum deposited on charcoal andchloroplatinic acid and its derivatives are the platinum catalysts usedpreferentially.

The hydrosilylation reaction can be carried out in the absence of asolvent or by bringing the reactants and, if appropriate, the catalyst,into contact in an organic medium consisting of a solvent or a diluentwhich is inert under the reaction conditions. As such there mayespecially be used saturated aliphatic hydrocarbons such as pentane,hexane and heptane; saturated cycloaliphatic hydrocarbons such ascyclohexane; aromatic hydrocarbons, such as benzene and toluene;halogenated hydrocarbons such as chloroform, dichloroethane andchlorobenzene; alcohols such as ethanol, propanol and isopropanol;ethers, such as tetrahydrofurane; and esters, such as methyl acetate,ethyl acetate and butyl acetate. The choice of the reaction mediumdepends on the nature of the starting reactants and on the temperatureat which the reaction takes place. The reaction can take place insolution or in suspension depending on whether one or both reactants aresoluble or insoluble in the chosen medium.

The relative amounts of the compounds of the formula (XVIII), which willhereafter be referred to as "dialkenylsilane monomer" or"dialkenylsilane" and of the α,ω-dihydrogenopolysiloxane, which willhereafter be referred to as "dihydrogeno monomer", can vary within widelimits. Thus, the relative amount of the reactants, expressed by theratio of the number of alkenyl groups introduced by the dialkenylsilanemonomer to the number of active hydrogen atoms introduced by thedihydrogeno monomer can vary for example from 2 to 0.5.

However, to obtain polymers of high molecular weight it is preferablethat the ratio defined above should be close to 1, though a slightexcess of one or other of the reactants can be used. Thus the ratio ofalkenyl group/H is preferably from 1.2 to 0.8. In this case themolecular weight of the thermoplastic elastomer of the invention can,where necessary, be adjusted to the desired value by using a chainstopper consisting of a silicon compound containing a single .tbd. Si--Hgroup or consisting of an organic or organo-silicon compound containingonly one ethylenic double bond.

Though any compound having a .tbd. Si--H group can be used as the chainstopper, the following should be mentioned particularly:trimethylsilane, triethylsilane, tri-n-propylsilane anddiethylmethylsilane.

Amongst the chain stoppers having an alkenyl group, organo-siliconcompounds such as trimethylvinylsilane, triethylvinylsilane andallyltrimethylsilane are used preferentially, though it is possible, touse organic monounsaturated compounds such as vinyl acetate, styrene orallylbenzene.

The amount of chain stopper is decided as a function of the desiredmolecular weight of the thermoplastic elastomer, in accordance with therules well-known in polymer chemistry to those skilled in the art.

If a catalyst is used to carry out the hydrosilylation reaction, theamount employed can vary within very wide limits depending on the natureof the catalysts, the nature of the reactants employed and the reactionconditions. Where a compound which generates free radicals is used, itis possible to use, for example, from 1 × 10⁻⁴ to 0.1 mol of catalystper mol of dialkenylsilane monomer, though it is possible, withoutdisadvantage, to go outside these limits. If the catalyst is one of theabovementioned metals or a derivative of these metals, especiallyplatinum, the amount of catalyst, expressed as gram atoms of metal peralkenyl group present in the dialkenyl monomer is suitably from 10⁻⁶ to10⁻¹ gram atom of metal per alkenyl group and preferably from 10⁻⁵ to10⁻².

As has already been indicated, the reaction temperature can vary withinwide limits depending on whether the reaction is carried out in thepresence or absence of a catalyst or, in the former case, depending onthe nature and amount of catalyst employed. Overall, the temperature canvary eg. from 0° to 300° C and preferably from 20° to 250° C. The use ofplatinum catalysts makes it possible to work at temperatures of theorder of 10° to 200° C. The reaction can also be carried out at apressure above, below or equal to atmospheric pressure.

To prepare the thermoplastic elastomers of the formula (XVII), in whichR" is an arylene radical containing one or more functional groups suchas specified earlier, it is preferable to employ compounds of theformula (XVIII), in which the functional groups carried by the aryleneradicals R" are inert towards the dihydrogenosiloxane under the reactionconditions. To obtain compounds of the formula (XVII) in which R"represents an arylene radical substituted by a functional group capableof reacting with the dihydrogenosiloxane (for example an amine group), acompound of the formula (XVIII) is employed, in which the functionalgroup or groups carried by the arylene groups R" are blocked by inertgroups and are then liberated by treating the polymer obtained afterhydrosilylation (for example by hydrogenation of nitro groups to aminegroups, in a known manner).

As specific examples of dialkenylsilane monomers of the formula XVIIIwhich can be employed for the preparation of the thermoplasticsilicon-based elastomers there may be mentioned specifically thoserepresented by the formulae (1), (2), (3), (4), (5), (6), (7), (8), (9),(10), (11), (12), (13), (14), (15), (16), (17), (18), (19), (20), (21),(22) and (23).

The α-ω-dihydrogenopolysiloxanes of the formula (XIX) employed ascomonomers for the preparation of the thermoplastic elastomers are knownproducts obtained in accordance with the usual processes of thechemistry of the silicones. For example, it is possible to hydrolyse themonohalogenodiorganosilane, such as monochlorodimethylsilane, orcohydrolyse a monohalogenodiorganosilane, a dihalogenodiorganosilaneand/or a cyclic polydiorganosiloxane such asoctamethylcyclotetrasiloxane; it is also possible to react amonohalogenodiorganosilane with an α,ω-dihydroxypolysiloxane of avariety of molecular weights or an α,ω-dialkoxypolysiloxane; further, itis possible to react a dihydrogenodiorganosiloxane with anα,ω-dihydroxypolysiloxane or an α,ω-dihalogenodiorganosiloxane with ametal hydride such as lithium aluminium hydride.

They can also be obtained by cationic polymerisation of anoctaorganocyclotetrasiloxane such as octamethylcyclotetrasiloxane withan α,ω-dihydrogenomonosiloxane such asα,ω-dihydrogenotetramethylsiloxane.

The molecular weight of the α,ω-dihydrogenosiloxane of the formula (XIX)is determined by the value of n, which can vary between 0 and 2,000. Ingeneral, compounds in which n is from 3 to 500 and preferably from 10 to200 and especially from 10 to 80 are used.

The α,ω-dihydrogenopolysiloxane can be a homopolysiloxane or a copolymerderived from two or more dihalogenodiorganosiloxanes. The copolymers canbe either compounds in which the various units are arranged as random orblock copolymers.

As specific examples of compounds of the formula (XIX) there may bementioned: dihydrogenotetramethyldisiloxane,dihydrogenodiethyldimethyldisiloxane,dihydrogenodiphenyldimethyldisiloxane or the compounds of the formula:

    ______________________________________                                        H(CH.sub.3).sub.2SiO[CH.sub.3 C.sub.6 H.sub.5 SiO]Si(CH.sub.3).sub.2 H        H(CH.sub.3).sub.2SiO[(C.sub.6 H.sub.5).sub.2SiO]Si(CH.sub.3).sub.2 H          H(CH.sub.3).sub.2SiO[(CH.sub.3).sub.2SiO].sub.25Si(CH.sub.3).sub.2 H          H(CH.sub.3).sub.2SiO[(CH.sub.3).sub.2SiO].sub.50 Si(CH.sub.3).sub.2 H         H(CH.sub.3).sub.2SiO[(CH.sub.3).sub.2SiO].sub.2000Si(CH.sub.3).sub.2 H        H(CH.sub.3)(C.sub.6 H.sub.5)SiO[(CH.sub.3)(C.sub.6 H.sub.5)SiO].sub.100Si(    CH.sub.3)(C.sub.6 H.sub.5) H                                                  H(CH.sub.3)(C.sub.3 H.sub.4 F.sub.3) SiO[(CH.sub.3)(C.sub.3 H.sub.4           F.sub.3) SiO].sub.40Si(CH.sub.3)(C.sub.3 H.sub.4 F.sub.3) H                   H(CH.sub.3).sub.2 SiO[ (C.sub.6 H.sub.4 Cl)(CH.sub.3)SiO].sub.30Si(CH.sub.    3).sub.2 H and                                                                H(CH.sub.3).sub.2SiO[(C.sub.2 H.sub.4 CN)(CH.sub.3)SiO].sub.20Si(CH.sub.3)    .sub.2 H                                                                      ______________________________________                                    

To prepare the thermoplastic elastomers according to the invention it ispossible, as has already been mentioned above, to employ one or moredialkenylsilane monomers (XVIII) together with one or moreα,ω-dihydrogenopolysiloxanes (XIX). In the latter case it is possible toreact 2 or more than two monomers (XVIII) or (XIX). This givescopolymeric thermoplastic elastomers. It is also possible to obtainblock copolymers by reacting a thermoplastic elastomer containing aplurality of recurring units of the formula (XVII) and having, at eachend of the chain, a monoalkenylsilane unit or a hydrogenosiloxane unit,with a thermoplastic elastomer containing a plurality of recurring unitsof the formula (XVII) different from those of the first elastomer andterminated by hydrogenosiloxane or monoalkenylsilane units,respectively.

The thermoplastic elastomers according to the invention can be used inall the fields where silicone elastomers are conventionally used, asthey retain the properties of the latter, but also in other fields whichare those where thermoplastic polymers are used because of the case withwhich they may be employed. They can be converted into various mouldedarticles by extrusion or injection in the molten state, or by stamping.They are particularly suitable for the production of films or of fibres.They can also be converted into finished articles by starting from theirsolutions in organic solvents.

Before being used, the thermoplastic elastomers according to theinvention can be mixed with the usual additives such as pigments fillerssuch as the various types of silica, titanium oxide and carbon blacks,plasticisers or heat stabilisers and light stabilisers.

The examples which follow illustrate the invention and show how it canbe put into practice; all temperatures are given in degrees Centigrade.

EXAMPLE 1

64.4 g of sodium p-nitrophenate are dissolved in 203 g ofN-methylpyrrolidone and this solution is introduced into a flask. Afterheating to 90° C, 53.8 g of dimethylvinylchloromethylsilane are run inover the course of 13 minutes and 10 cm³ of N-methylpyrrolidone areadded. The reaction mixture is kept at about 100° for 20 hours, thesodium chloride is filtered off and the N-methylpyrrolidone is distilledunder reduced pressure. The residual reaction mixture is dissolved inether and the ether solution is washed with an aqueous sodium carbonatesolution. After distilling the ether, 91 g of a yellow productcrystallising at 34° are obtained. The percentage analysis and infraredanalysis show that the compound isp-(dimethylvinylsilylmethoxy)-nitrobenzene. ##STR79##

EXAMPLE 2

102.8 g of p-aminobenzoic acid and 500 cm³ of N-methylpyrrolidone areintroduced into a flask and after the material has dissolved 60.7 g oftriethylamine are introduced at 25°. 67.4 g ofvinyldimethylchloromethylsilane are then run in, over the course of 3hours, into the mixture heated to 130°. The whole is kept at 130° for 21hours and after cooling 64.8 g of triethylamine hydrochloride arefiltered off.

The N-methylpyrrolidone is removed by distillation and the distillationresidue is taken up in 200 cm³ of ether and then washed with an aqueoussodium carbonate solution. The ether is removed by distillation andafter rectification a fraction weighing 78.8 g, of boiling point₀.35 :153°-154°, which corresponds top-(dimethylvinylsilylmethoxycarbonyl)-aminobenzene, is obtained. The IRspectrum, the determination of the amine groups and the microanalysisare in agreement with the formula: ##STR80##

p-(Dimethylvinylsilylmethoxycarbonyl)-aminobenzene crystallises at 30°.

EXAMPLE 3

760 g of methyl p-hydroxybenzoate and 850 ml of N-methylpyrrolidone areintroduced into a flask and a methanolic solution of sodium methylate,prepared from 960 g of methanol and 115 g of sodium, is run in over thecourse of 2 hours 20 minutes at between 82° and 100°. The methanol isthen removed by distillation and 672 g ofvinyldimethylchloromethylsilane are run over the course of 1 hour 5minutes at between 108° and 128°.

After distilling the N-methylpyrrolidone, the distillation residue istaken up with 2 l of cyclohexane and washed with water, and the methylp-(dimethylvinylsilylmethoxy)-benzoate is rectified. This gives 1,136 gof a fraction of boiling point₀.1 : 110°-113°, having a melting point of25.5°.

Treatment of the methyl p-(dimethylvinylsilylmethoxy)-benzoate with asodium hydroxide solution containing 100 g of sodium hydroxide, 250 g ofwater and 1,000 ml of methanol gives the sodium salt ofp-(dimethylvinylsilylmethoxy)-benzoic acid.

After acidifying a solution containing the sodium salt ofp-(dimethylvinylsilylmethoxy)-benzoic acid, a white product melting at118° is isolated by filtration; it corresponds top-(dimethylvinylsilylmethoxy)-benzoic acid: ##STR81##

EXAMPLE 4

354 g of p-(dimethylvinylsilylmethoxy)-benzoic acid, prepared inaccordance with the procedure described in Example 3, are introducedinto a flask and 357 g of thionyl chloride are run in over the course of40 minutes at between 28° and 29°. The reaction mixture is then heatedand kept at 102° for 1 hour. Rectification gives a fraction of 344 g, ofboiling point₀.1 126°-127°, corresponding to the chloride ofp-(dimethylvinylsilylmethoxy)-benzoic acid: ##STR82##

EXAMPLE 5

26.5 g of sodium are introduced gradually into a flask containing 224 gof methanol and this solution is run, over the course of 50 minutes,into another flask containing 175 g of methyl p-hydroxybenzoate and 200ml of N-methylpyrrolidone. Whilst this material is being run in, themethanol is distilled. When the addition is complete, 171 g ofallyldimethylchloromethylsilane are introduced over the course of 7minutes, the reaction mixture being kept at 100°. After rectification, afraction of 215 g corresponding to methylp-(dimethylallylsilylmethoxy)-benzoate is obtained: ##STR83##

The sodium salt of p-(allyldimethylsilylmethoxy)-benzoic acid, andp-(allyldimethylsilylmethoxy)-benzoic acid itself (melting point = 93°C) are prepared according to a process analogous to that described inExample 3.

EXAMPLE 6

25.2 g of ethyl thioglycollate and 100 ml of methanol are introducedinto a flask and 41.7 ml of sodium methylate (a 4.8 M solution inmethanol) are run in over the course of 15 minutes at 20°. 26.94 g ofdimethylvinylchloromethylsilane are then added over the course of 5minutes, after which the methanol is distilled. After filtering thesodium chloride and rectifying the filtrate, a fraction of 43.2 g, ofboiling point₁ : 86°-88° is obtained, which corresponds to ethyl(vinyldimethylsilyl)-methylmercaptoacetate: ##STR84##

EXAMPLE 7

775 g of stannous chloride and 700 g of hydrochloric acid (d = 1.19) areintroduced into a flask and a solution ofp-(vinyldimethylsilylmethoxy)-nitrobenzene prepared according to theprocedure of Example 1 and containing 118.5 g of the nitro derivativeand 150 cm³ of ethanol is then run in over the course of 50 minutes atbetween 30° and 45°.

The reaction mixture is kept at 45° for 2 hours. After cooling, thefollowing are carried out: filtration of the tin tetrachloride, washingwith water, neutralisation with a concentration sodium hydroxidesolution and filtration of the precipitate formed. This precipitate isdissolved in excess sodium hydroxide solution.

After extracting with ether, removing the ether by evaporation, andrectification, a fraction, 79.8 g, of boiling point₀.8 : 115°-117°, ofp-(vinyldimethylsilylmethoxy)-aminobenzene is obtained: ##STR85##

EXAMPLE 8

34.7 g of xylene, 0.4 g of tetramethylurea and 16.15 g of phosgene areintroduced into a flask, the mixture is heated under reflux and asolution consisting of 30.6 g ofp-(dimethylvinylsilylmethoxy)-aminobenzene, prepared in accordance withthe method described in Example 2, and 34.7 g of xylene, is run in overthe course of 30 minutes. The reaction mixture is kept at the refluxtemperature throughout the addition. Thereafter, heating under reflux iscontinued for 30 minutes.

Rectification under reduced pressure gives 28 g of a colourless oil ofboiling point₀.2 = 110°, corresponding to1-isocyanato-4-(dimethylvinylsilylmethoxy)-benzene: ##STR86##

EXAMPLE 9

91.5 g (0.6 mol) of methyl p-hydroxybenzoate and 100 cm³ of methanol areintroduced into a 500 cm³ flask equipped with a mechanical stirringsystem, a dropping funnel, a reflux condenser, a thermometer and aheating device.

The contents of the flask are heated to the reflux temperature and asolution of 24 g of NaOH in 200 cm³ of methanol is added over the courseof 40 minutes. Thereafter, the methanol is removed by distillation and200 cm³ of N-methylpyrrolidone are added. The contents of the flask areheated to 113°-127° C and 88 g of methyldivinylchloromethylsilane areadded. The mixture is kept under these conditions for 1 hour 30 minutes.

The N-methylpyrrolidone is then driven off by distillation. The residueis taken up in 250 cm³ of cyclohexane and this solution is thereafterwashed with water, and then distilled. 146 g of a production having thefollowing characteristics are thus isolated:

Boiling point/0.5 mm Hg: 125°-130° C

Melting point: 18° C n₂₀ ^(D) : 1.532 d 20/4: 1.0525

The percentage analysis of the product is as follows:

C % = 63.07

h % = 6.94

si % = 10.7

Vinyl % = 20.6

The infra-red spectrum corresponds to that of methylp-(divinylmethylsilylmethoxy)-benzoate.

EXAMPLE 10

The sodium salt of p-(divinylmethylsilylmethoxy)-benzoic acid isprepared by treating 105 g of methylp-(divinylmethylsilylmethoxy)-benzoate with a solution of 20 g of NaOHin 50 cm³ of water and 200 cm³ of methanol. After acidification, a whiteproduct (98 g) of melting point 104° C is isolated by filtration; itspercentage composition is as follows:

C % = 62.05

h % = 6.37

si % = 10.56

Vinyl % = 21.24

The compound is identified as beingp-(divinylmethylsilylmethoxy)-benzoic acid.

74.5 g of the acid obtained above are introduced into the apparatusdescribed in Example 9 and 71.5 g of thionyl chloride (0.6 mol) areadded over the course of 15 minutes at between 25° and 28° C. Thereaction mixture is then kept at the reflux temperature for 1 hour.Distillation gives 74 g of a fraction which passes over at between 117°and 120° C under 0.06 mm of mercury. The product was identified as beingthe chloride of p-(divinylmethylsilylmethoxy)-benzoic acid. Its meltingpoint is 22° C.

EXAMPLE 11 Preparation of the compound (3)

10.35 g of 1-amino-4-(vinyldimethylsilylmethoxy)-benzene (compareExample 7), 5.05 g of triethylamine and 50 cm³ of carbon tetrachlorideare introduced into a three-neck 250 cm³ flask equipped with amechanical stirrer, a reflux condenser, a dropping funnel and athermometer, the whole being kept under an atmosphere of dry nitrogen.

The reaction mixture is cooled to -4° C whilst stirring. A solution of5.22 g of terephthaloyl chloride in 17 cm³ of acetone is introduced intothe dropping funnel and is then run in uniformly over the course of 27minutes. During the addition, the temperature is kept at between -4° and+2° C. The reaction mixture is left for a further 1 hour 30 minutes,whilst being stirred vigorously.

Thereafter, the reaction mixture is poured into 100 cm³ of water; theprecipitate formed is filtered off, washed with 4 times 40 cm³ of amixture of water and acetone, again filtered off and then dried at 110°C under reduced pressure (5 mm Hg).

This gives 12.90 g of a product of melting point (Kofler) 315° C.

The following analyses are carried out on the isolated product:percentage analysis:

C % = 66.09

h % = 6.53

n % = 5.06

nmr spectrum: the ratio of the protons of the vinyl group and thearomatic protons is in accordance with theory. IR spectrum: thefollowing different absorption bands are observed:

    ______________________________________                                        SiCH CH.sub.2     1,010 and 950 cm.sup.-1                                     SiCH.sub.3        1,250 - 830 cm.sup.-1                                       NH                3,280 cm.sup.-1                                             CO                1,640 cm.sup.-1                                              ##STR87##        1,230 and 1,110 cm.sup.-1                                   ______________________________________                                    

EXAMPLE 12 1. Preparation of the compound (4)

65.5 g of 4,4'-diamino-diphenylmethane dissolved in 350 ml of anhydrouschloroform and 74 g of triethylamine are introduced into a 500 cm³three-neck flask equipped as in Example 11.

The reaction mixture is cooled to 0° C whilst stirring. 168 g of thechloride of p-(dimethylvinylsilylmethoxy)-benzoic acid are run in overthe course of 1 hour 30 minutes. During the addition the temperature iskept at 0° ± 1° C.

The solution is then run into 400 cm³ of water whilst stirring. Theorganic layer is separated off, washed with 3 times 200 cm³ of water,dried over anhydrous magnesium sulphate and then evaporated to constantweight.

This gives 219 g of a crude product which is treated with 10 g ofcharcoal and recrystallised from 500 cm³ of absolute ethanol.

171 g of4,4'-N,N'-bis-[p-(vinyldimethylsilylmethoxy)-benzoyl]-diaminodiphenylmethane,of melting point 154° C, are isolated in this way.

The following analyses are carried out on the isolated product:percentage analysis:

C%: 69.90

h%: 6.76

n%: 4.58

si%: 8.75

Nmr spectrum: in agreement with formula (4). determination of free aminegroups: this determination proves negative.

EXAMPLE 13 Preparation of the compounds (17) and (18)

41.4 g of 1-amino-4-(vinyldimethylsilylmethoxy)-benzene prepared inaccordance with the method described in Example 7, and 100 cm³ ofdimethylformamide containing 0.02% of water, are introduced into a 500cm³ three-neck flask equipped as in Example 11.

The reaction mixture is heated to 60° C whilst stirring and 21.8 g ofpyromellitic anhydride are added gradually over the course of 20minutes, in small fractions of 3 g.

A limpid yellow solution of the compound (17 ) is obtained.

Stirring, and heating at 60° C, is continued for a further hour, 30.6 gof acetic anhydride are added over the course of 5 minutes and 6.2 cm³of pyridine are then run in over the course of 5 minutes. As from theend of the addition of the pyridine, a yellow precipitate forms. Heatingis continued for 1 hour 45 minutes, the temperature being kept atbetween 60° and 70° C.

After cooling, the precipitate formed is filtered off, washed with 4times 40 cm³ of acetone, suction-drained and dried at about 110° C underreduced pressure (25 mm Hg) for 8 hours.

50.2 g of a crude product are obtained, and a 45 g portion isrecrystallised by dissolving in 2,000 cm³ of dimethylformamide at theboil.

43.1 g of yellow crystals melting at 380° C, with decomposition, areobtained.

The following analyses are carried out on the recrystallised product:percentage analysis:

C%: 64.42

h%: 5.60

n%: 4.79

ir spectrum

Co: 1,785 - 1725 cm⁻¹

Si--CH ═ CH₂ : 1,010 and 960 cm⁻¹

Si--(CH₃)₂ : 860 and 800 cm⁻¹

thin layer chromatography (TLC): a spot with Rf = 0.62 is obtained bychromatography on a silica plate, the eluant being a mixture of ethylacetate (90%) and benzene (10%).

EXAMPLE 14 Preparation of the compound (5)

41.1 g of 1-amino-4-(vinyldimethylsilylmethoxy)-benzene synthesised asin Example 1 and 50 cm³ of dimethylformamide are introduced into a 500cm³ three-neck flask equipped as in Example 11.

The mixture is stirred and a solution of 25 g of4,4'-diisocyanato-diphenylmethane in 75 cm³ of dimethylformamide is runin slowly over the course of 30 minutes. During the addition, thetemperature of the reaction mixture is kept at between 7° and 13° C.

The heating is then continued for 3 hours at 20°-22° C. The colourlesssolution is then run, whilst stirring, into 400 cm³ of iced distilledwater. After allowing the phases to separate for 2 hours, theprecipitate is filtered off and then washed with 5 times 75 cm³ ofwater.

54 g of a crude product are obtained and are purified by dissolving in200 cm³ of dimethylformamide and treating with 200 cm³ of acetonitrileso as to bring about the precipitation. The mixture is cooled for 2hours in an ice bath and the precipitate is filtered off, then washedwith 300 cm³ of acetonitrile, suction-drained and dried at 110° C under1 mm Hg for 8 hours.

53 g of a white product which melts at 280° C, with decomposition, areobtained.

The following analyses are carried out on the precipitated product:percentage analysis:

C%: 66.65

h%: 6.65

n%: 8.42

ir spectrum:

    ______________________________________                                        NH                 3,300 cm.sup.-1                                            CO                 1,665 cm.sup.-1                                            SiCHCH.sub.2       1,010 and 960 cm.sup.-1                                    Si(CH.sub.3).sub.2 830 cm.sup.-1                                               ##STR88##         1,220 cm.sup.-1                                            ______________________________________                                    

Tlc: a spot of Rf = 0.87 is obtained, the elution solvent being amixture of chloroform (96%) and methanol (4%).

EXAMPLE 15 Preparation of the compound (6 )

6.36 g of ethylene glycol terephthalate and 30 cm³ of pyridine areintroduced into the apparatus previously described in Example 11.

This solution is cooled to about 5° C and 12.74 g of the chloride ofp-(dimethylvinylsilylmethoxy)-benzoic acid synthesised as in Example 3,are introduced in small fractions over the course of 12 minutes.

The temperature of the reaction mixture rises to 10° C at the end of theaddition. The heating of the solution is increased progressively, thesolution becoming limpid at about 76° C, and is continued at 110° C for3 hours.

The mixture is cooled whilst stirring. A copious precipitate of pyridinehydrochloride forms, which is filtered off, washed with twice 5 cm³ ofanhydrous pyridine and then suction-drained. The filtrate is poured into300 cm³ of iced water, whilst stirring. After allowing the phases toseparate for 1 hour, the precipitate is filtered off, then washed with300 cm³ of water, suction-drained and dried.

This gives 16.4 of white crystals melting at 70° C, which are thenrecrystallised from 100 cm³ of isopropanol. After filtration and drying,14.6 g of white crystals melting at 72°-74° C are obtained.

The following analyses are carried out on the recrystallised product:percentage analysis:

C%: 62.76

h%: 6.53

si%: 7.69

IR spectrum:

    ______________________________________                                        CO                 1,730 and 1,710 cm.sup.-1                                   ##STR89##         1,250 cm.sup.-1                                            SiCHCH.sub.2       1,020 and 965 cm.sup.-1                                    SiCH.sub.3         830 cm.sup.-1                                              ______________________________________                                    

Tlc: a spot of Rf = 0.44 is obtained, the eluant being benzene.

EXAMPLE 16 Preparation of the compound (7)

20 g of 1-amino-4-(vinyldimethylsilylmethoxycarbonyl)-benzene, 8.6 g oftriethylamine and 50 cm³ of acetone are introduced into the apparatuspreviously described in Example 11.

A solution of 8.8 g of terephthaloyl chloride dissolved in 100 cm³ ofacetone is introduced into the dropping funnel and is then run into thereaction mixture, kept at 35° C. After adding 11 cm³ of the solution ofterephthaloyl chloride, a white precipitate forms.

The addition is continued and lasts for 1 hour 15 minutes.

The reaction mixture is then brought to the boil and kept at its boilingpoint, namely 58° C, for 1 hour.

After cooling, the precipitate is filtered off on a glass frit and isthen washed with 5 times 50 cm³ of water, suction-drained and then driedfor 4 hours at 100° C under 25 mm pressure.

21.2 g of product are thus obtained.

The filtrate is precipitated by 500 cm³ of water, which makes itpossible to obtain a further 3.57 g of product.

10 g of product originating from the first filtration are recystallisedfrom 250 cm³ of chlorobenzene, making it possible to obtain 8.9 g ofpearlescent crystals identified as beingN,N'-bis-p-[(vinyldimethylsilyl)methoxycarbonyl)-phenyl]-terephthalamideof melting point 260° C.

The following analyses are carried out on the purified product:percentage analysis

C%: 64.38

h%: 6.06

n%: 4.97

si%: 9.1

Nmr specturm: in agreement with formula (7).

    ______________________________________                                        CO (conjugated ester)                                                                         1,700 cm.sup.-1                                               CO (secondary amide)                                                                          1,665 cm.sup.-1                                               NH              3,350 cm.sup.-1                                               C--NH           1,530 cm.sup.-1                                               Si--CH.sub.3    1,250 cm.sup.-1                                               Si--CH=CH.sub.2 1,010 cm.sup.-1 and 955 cm.sup.-1                             aromatic disubstitution                                                       and Si--(CH.sub.3).sub.2                                                                      830-850 cm.sup.-1                                             ______________________________________                                    

EXAMPLE 17 1. Preparation of the compound (19)

4.25 g of 1,3-bis-(3-p-aminophenoxy-propyl)-tetramethyldisiloxane, 1.84g of triethylamine and 50 cm³ of acetone are introduced into a 100 cm³three-neck flask equipped as in Example 11.

4.63 g of the chloride of p-(dimethylvinylsilylmethoxy)-benzoic acidprepared in accordance with the procedure of Example 3 and 30 cm³ ofacetone are introduced into the dropping funnel.

The reaction mixture is stirred and cooled to 3° C.

Thereafter, the solution of the acid chloride is run in over the courseof 15 minutes. The temperature rises to 6° C at the end of the addition.

Thereafter, the reaction mixture is heated to 50° C and this temperatureis maintained for 1 hour.

After cooling, the reaction mixture is poured into one liter of water,whilst stirring. The precipitated formed is filtered off, washed with100 cm³ of water and then dried.

7.43 g of a crude product are obtained.

6 g of this compound are recrystallised from 200 cm³ of methanol.

5.1 g of a whitish solid of melting point 145° C are collected.

3.25% of nitrogen and 7.53% of hydrogen are found by elementaryanalysis.

TLC gives a single spot of Rf = 0.74, the eluant being a mixture oftoluene (90%) and ethyl acetate (10%).

2. Preparation of1,3-bis-(3-p-aminophenoxy-propyl)-tetramethyldisiloxane

The coupling agent is synthesised as follows:

66 g of 4-allyloxy-nitrobenzene and 0.07 cm³ of a solution ofchloroplatinic acid in alcohol, containing 30 mg of platinum/cm³, areintroduced into a 250 cm³ three-neck flask equipped with a mechanicalstirrer, a condenser, a dropping funnel and a thermometer, the wholebeing kept under an atmosphere of nitrogen.

25 g of tetramethyl-1,3-dihydrogenodisiloxane are introduced into thedropping funnel and the addition of 5 cm³ to the reaction mixture isstarted, whilst stirring at ambient temperature. The reaction mixture isthen heated to about 100° C and the addition is continued; thetemperature rises sharply to about 200° C. The reaction mixture iscooled to 130° C and this temperature is maintained for 30 minutes.

After cooling, a viscous mass is obtained, which is run, whilststirring, into 2,000 cm³ of ethanol.

A precipitate forms, which is filtered off and dried.

18.8 g of a compound melting at 80° C, on which the following analysesare carried out, are obtained: IR spectrum:

    ______________________________________                                         ##STR90##         1,510-1,330 cm.sup.-1                                      SiCH.sub.3         1,250 cm.sup.-1                                             ##STR91##         1,265 cm.sup.-1                                            SiO                1,080 cm.sup.-1                                            ______________________________________                                    

Nmr specturm: in accordance with theory.

The reduction of the nitro group is carried out in the following manner:

10 g of the compound prepared above, 50 cm³ of ethyl acetate and 0.2 gof ADAMS platinum containing 83.6% of platinum are introduced into a 125cm³ stainless steel autoclave.

The autoclave is flushed with nitrogen. Hydrogen under a pressure of 50bars is introduced into the reaction mixture which is kept at ambienttemperature. After 15 minutes, the pressure drops to 28 bars and theinitial pressure is re-established.

After 35 minutes, the mixture is heated to 55° C for 1 hour.

After cooling the autoclave, a catalyst suspension is obtained, which isthen separated by filtration.

The solvent is evaporated under reduced pressure.

9.15 g of an amine liquid are obtained, containing 0.0392 mol of aminegroup according to determination by means of perchloric acid.

TLC on a silica plate, the elution solvent being ethyl acetate, gives aspot of Rf = 0.34.

EXAMPLE 18 Preparation of the compound (20)

45 g (0.1 M) of bis-(4-amino-4'-benzamido-phenyl)-methane, followed by250 cm³ of N-methylpyrrolidone, are introduced into a 500 cm³ 3-neckflask equipped with a mechanical stirrer, a thermometer, a condenser, adropping funnel and a nitrogen inlet tube.

51 g (0.2 M) of the chloride of (dimethylvinylsilylmethoxy)-benzoicacid, previously heated to about 50° C, are run, over the course of 1hour, into the pasty suspension thus obtained, which is kept at about 5°to 10° C.

The suspension dissolves gradually.

The brown reaction solution is kept at ambient temperature, whilststirring, for a further 2 hours. The reaction mixture is thenprecipitated in 1.5 l of vigorously stirred iced water. The beigeprecipitate is filtered off and then washed with water.

On dissolving the cake in hot dimethylformamide, filtering hot and thencooling the filtrate, 74 g of light beige crystalline product areobtained.

The product thus prepared has a melting point of 315° C. Its infra-redspectrum exhibits the characteristic bands of the compound of theformula (20). Analysis by thin layer chromatography shows that thisproduct is free from impurity. The percentage analysis for carbon,hydrogen and nitrogen gave the following results:

C% = 70.19

h% = 5.97

n% = 6.42

example 19 preparation of the compound (21)

20 g (0.05 mol) of bis-(4-aminophenyl) terephthalate and 75 cm³ ofN-methylpyrrolidone are introduced into the apparatus used in Example 8.The solution obtained is kept at 5°-10° C whilst a solution of 25.5 g(0.1 mol) of the chloride of p-(vinyldimethylsilylmethoxy)-benzoic acidin 25 cm³ of N-methylpyrrolidone is added over the course of 1 hour. Themixture is then kept at 20° C for 3 hours, after which 500 cm³ of coldwater are added to the reaction mixture. This gives a yellow precipitatewhich is filtered off and then washed on the filter. Thereafter theprecipitate is dissolved in hot dimethylformamide, the solution isfiltered and the filtrate is then cooled to 20° C. This gives a whitecrystalline product which weighs 27.5 g after drying to constant weightin vacuo.

This product has a melting point of 301° C and exhibits an infra-redspectrum which agrees with that of the compound of the formula (21). Itdoes not contain impurities and the percentage analysis of the elementsC, H and N gave the following results:

C% = 66.65

h% = 5.65

n% = 3.41

example 20 preparation of the compound (22)

24 g (0.1 mol) of 4'-aminophenyl 4-aminobenzoate and 100 cm³ ofN-methylpyrrolidone are introduced into the apparatus described inExample 18.

A suspension is obtained, which is kept at between 5° and 10° C whilst asolution of 51 g (0.2 mol) of the chloride ofp-(vinyldimethylsilylmethoxy)-benzoic acid in 50 cm³ ofN-methylpyrrolidone is added thereto over the course of 1 hour. Thereaction solution is kept at 20° C for 2 hours after the end of theaddition, and is then added to 800 cm³ of iced water whilst stirring. Aprecipitate is thus formed, which is filtered off and then washed withwater on the filter. The precipitate is dissolved in hot dioxane, thesolution is filtered and the filtrate is cooled to 20° C. This gives 56g of a crystalline white product free from impurities, which has amelting point of 213° C and of which the infra-red spectrum agrees withthat of the compound of the formula (22). The percentage analysis of theelements C, H and N gave the following results:

C% = 66.59

h% = 6.18

n% = 4.04

example 21 preparation of the compound (23)

21.6 g of p-phenylenediamine and 200 cm³ of N-methylpyrrolidone areintroduced into the apparatus described in Example 18.

The solution is cooled to 5°-10° C and a solution of 102 g of thechloride of p-(vinyldimethylsilylmethoxy)-benzoic acid in 100 cm³ ofN-methylpyrrolidone is added over the course of 1 hour.

The contents of the flask are then heated to 60° C and kept at thistemperature for 1 hour.

The hot reaction solution is added to 1 l of iced water whilst stirring.A beige precipitate is obtained, which is filtered off, washed withwater and then dissolved in hot dioxane.

This solution is filtered and the filtrate is then cooled to 20° C.

A white crystalline precipitate is obtained, which is filtered off anddried to constant weight. 83.5 g of a product of melting point 255° C,which is free from impurities and of which the infra-red spectrum agreeswith that of the compound of the formula (23), are thus isolated.

The percentage analysis of the elements C, H and N gave the followingresults:

C% = 65.13

h% = 6.75

n% = 5.25

example 22 1. preparation of the compound of the formula (24)

19.8 g (0.1 mol) of 4,4'-diaminodiphenylmethane, 150 cm³ of chloroformand 23 g of triethylamine are introduced into the apparatus described inExample 18.

The contents of the flask are cooled to 4° C and a solution of 53.5 g(0.2 mol) of the chloride of p-(divinylmethylsilylmethoxy)-benzoic acidin 100 cm³ of chloroform is then added over the course of 1 hour 50minutes.

The reaction mixture is then washed three times with 60 cm³ of distilledwater after which the chloroform is driven off by distillation. Theresidue obtained is recrystallised from absolute ethanol. This gives60.5 g of a white product free from impurities, which melts at 142° Cand of which the nuclear magnetic resonance spectrum agrees with that ofthe compound of the formula (24).

The percentage analysis of this product gave the following results:

C% = 70.66

h% = 6.69

n% = 3.95

si% = 8.31

EXAMPLE 23 Preparation of the thermoplastic elastomer

419 g of toluene, 108.14 g of an α,ω-dihydrogenopolydimethylsiloxane ofnumber-average molecular weight 2,150 and of viscosity 26.5 cst,measured at 25° C, which contains 0.093 atom of hydrogen per 100 g ofpolysiloxane (n = 28 in the formula I), and 31.7 g of4,4'-N,N'-bis-[p-(vinyldimethylsilylmethoxy)-benzoyl]-diaminodiphenylmethaneof the formula: ##STR92## are introduced into a 1 l cylindrical glassreactor equipped with a stirring system, a heating device, a thermometerand a reflux condenser.

The contents of the reactor are stirred under a nitrogen atmosphere andthen heated under reflux until a homogeneous solution is obtained. 3.3cm³ of a solution containing chloroplatinic acid (H₂ PtCl₆) inisopropanol (concentration: 3 × 10⁻⁶ gram atom of Pt/cm³) are thenadded. An immediate increase in the viscosity of the reaction mixture isobserved. The mixture is kept under these conditions for 4 hours and thetoluene solution is then cooled to 20° C.

The viscosity of the solution, adjusted to 20% by weight of solidscontent by addition of toluene, is 30 poises at 25° C.

A film is prepared by depositing, by means of a casting machine, auniform 0.5 mm layer of the solution of 25% solids content on a glassplate and then evaporating the solvent by heating to 80° C for 1 hour. Atransparent elastic film of 70μ thickness is obtained, the mechanicalproperties of which are as follows: breaking load determined inaccordance with French Standard Specification T 46,002: 88 kg/cm²elongation at break determined in accordance with French StandardSpecification T 46,007: 660%.

A sample of the film obtained above is dissolved in chloroform at aconcentration of 0.5 g/100 cm³. The inherent viscosity of this solution,measured at 25° C, is 65 cm³ /g.

The examination, by infra-red spectrometry, of the product obtainedmakes it possible to establish the absence of a band at 10.5μ whichcorresponds to the .tbd.Si--CH═CH₂ group and the presence of thefollowing bands:

3.05μ, corresponding to the --NH-- group

6.10μ, corresponding to the ##STR93## group and 6.64μ, corresponding tothe ##STR94## chain unit.

Furthermore, it was not possible to determine the active hydrogen bygasometric methods after treating the product with potash.

The polymer obtained above has a softening point of 160° C and aweight-average molecular weight Mw of 170,000, measured bylight-scattering on a solution in ethyl acetate; it corresponds to thestructure ##STR95##

EXAMPLE 24

A thermoplastic elastomer of the same structure as in Example 23 isprepared by following the same procedure but replacing the toluene by476 cm³ of butyl acetate. The total duration of the reaction is 5 hours.

The solution obtained, diluted to 20% by weight of solids by addition ofbutyl acetate, has a viscosity of 2 poises at 25° C.

The inherent viscosity of a sample of the reaction product measured on asolution of 0.5 g in 100 cm³ of chloroform at 25° C is 53 cm³ /g.

The polymer thus obtained has a softening point of 160° C. The breakingload and the elongation measured as in Example 1 are respectively 68kg/cm² and 600%.

The percentage analysis and the infra-red spectrum correspond to theproduct of Example 23.

EXAMPLE 25 Preparation of the thermoplastic elastomer with recurringunits: ##STR96##

4.088 g ofN,N'-bis-[p-(vinyldimethylsilylmethoxy)-phenyl]-terephthalamide, 8.36 gof an α,ω-dihydrogenopolydimethylsiloxane of number-average molecularweight 1,114, containing 0.181 atom of active hydrogen per 100 g ofpolymer, having a viscosity of 9.3 cst at 25° C, and containing about 15dimethylsiloxane units, and 43 cm³ of toluene are introduced into areactor equipped as in Example 23.

The contents of the reactor are heated to the reflux temperature and0.36 cm³ of a solution of chloroplatinic acid containing 8 × 10⁻⁶ gramatom of Pt/cm³ is then added. The terephthalamide dissolves in 7minutes. A further 0.90 cm³ of chloroplatinic acid is added and heatingis continued for 5 hours 30 minutes. The solution is very viscous;cooling gives a gel which is dispersed in 200 cm³ of methanol andstirred vigorously. The polymer obtained is filtered off and thenre-suspended in 200 cm³ of methanol. It is then filtered off and driedat 80° C under 2 mm of mercury.

This gives a product of softening point 190° C and of inherent viscosity32 cm³ /g, measured at 25° C on a solution of 0.5 g in 100 cm³ of CHCl₃.

The percentage composition and the infra-red spectrum correspond tothose of a polymer having the recurring unit mentioned above. It was notpossible to demonstrate the presence of active hydrogen which can bedetermined by gasometric methods after treating the product obtainedwith potash. The infra-red spectrum of the product no longer containsthe bands characteristic of the vinylsilyl group.

A sample is moulded by using the following procedure:

10 g of the polymer obtained above are introduced into a square mould ofsize 10 × 10 × 0.4 cm and the mould is placed between 2 sheets ofstainless steel. The whole is placed between the platens of a pressheated to 194° C, a pressure of 15 kg/cm² is then applied and the wholeis kept under these conditions for 15 minutes.

After cooling, a transparent elastic sheet is obtained, the mechanicalproperties of which are as follows: breaking load determined inaccordance with French Standard Specification T 46,002: 141 kg/cm²elongation at break determined in accordance with French StandardSpecification T 46,002: 396% tear strength in accordance with FrenchStandard Specification T 46,007: 45 kg/cm.

EXAMPLE 26

A thermoplastic elastomeric polymer derived fromN,N'-bis-[4-(vinyldimethylsilylmethoxy)-phenyl]-terephthalamide isprepared as follows:

3.17 g ofN,N'-bis-[4-p-(vinyldimethylsilylmethoxy)-phenyl]-terephthalamide,10.804 g of the α,ω-dihydrogenopolydimethylsiloxane used in Example 23,42 g of cyclohexane and 0.3 cm³ of a solution of H₂ PtCl₆ in toluene,containing 3.3 × 10⁻⁶ gram atom of Pt/cm³ are introduced into a reactorequipped as in Example 23 and the suspension obtained is heated to theboil. After 1 hour, an increase in the viscosity of the reaction mixtureis observed; heating is continued for 7 hours 30 minutes; the reactionmixture is then in the form of a homogeneous solution. It is cooled to20° C and the precipitation of a polymer swollen with solvent isobserved. The cooled mass is heated to 80° C to cause the polymer todissolve, and a film is then prepared as in Example 23 by casting thesolution on a plate heated to 80° C.

This gives a film of which the inherent viscosity at 25° C, measured ona solution of 0.5 g in 100 cm³ of chloroform, is 36 cm³ /g.

Its percentage composition and its infra-red spectrum correspond tothose of a polymer having the recurring unit: ##STR97##

The film obtained above has the following mechanical properties(measured as in Example 23):

breaking load: 48 kg/cm²

elongation at break: 275%

EXAMPLE 27 Preparation of a thermoplastic elastomer derived from theN,N'-bis-[p-(vinyldimethylsilylmethoxycarbonyl)-phenyl]-terephthalamideof the formula: ##STR98##

1.5 g of terephthalamide and 7.1 g of anα,ω-dihydrogenopolydimethylsiloxane of number-average molecular weight2,930, containing 0.068 atom of active hydrogen per 100 g of polymer, ofviscosity 48 cst at 20° C, and containing about 30 dimethylsiloxaneunits, are introduced into an apparatus equipped as in Example 23.

The contents of the flask are heated to 110° C and 0.3 cm³ of a solutionof hexachloroplatinic acid in toluene, containing 8 × 10⁻⁶ gram atom ofplatinum per cm³ is added, followed by an additional quantity ofchloroplatinic acid (1.9 × 10⁻⁵ gram atom of platinum). Heating iscontinued for 24 hours at 110° C and the solution is then cooled andpoured into 2 l of methanol, with vigorous stirring.

The precipitate is washed with 100 cm³ of methanol and then dried for 24hours at 80° C under reduced pressure (3 mm of mercury).

The inherent viscosity of the polymer measured at 25° C on a solution of0.5 g in 100 cm³ of chloroform is 30 cm³ /g. Its softening point is 120°C.

EXAMPLE 28 Preparation of the thermoplastic elastomer

67.47 g of toluene, 15.06 g of an α,ω-dihydrogenopolydimethylsiloxane ofnumber-average molecular weight 1,100 (n = about 13 in the formula I)and 7.42 g of4,4'-N,N'-bis-[p-(vinyldimethylsilylmethoxy)-benzoyl]-diaminobenzene ofthe formula ##STR99## are introduced into a 250 cm³ flask equipped witha stirring system, a thermometer, a reflux condenser and a heatingdevice.

The suspension is heated under reflux whilst stirring and 0.8 cm³ of asolution of chloroplatinic acid in toluene containing 3 × 10⁻⁶ gram atomof platinum per cm³ is then added. The reaction mixture becomes viscousand homogeneous. It is kept under reflux for 6 hours 15 minutes.

Following the procedure of Example 23, a film is prepared from thereaction solution. A white elastomer is thus obtained, having asoftening point of 190° C and an inherent viscosity of 40 cm³ /g,measured at 20° C on a solution containing 0.5 g in 100 cm³ ofchloroform.

The percentage composition and the infra-red spectrum correspond tothose of a polymer containing a plurality of recurring units of theformula: ##STR100##

EXAMPLE 29 Preparation of the thermoplastic elastomer with recurringunit: ##STR101##

40.11 g of dioxane, 10.21 g of an α,ω-dihydrogenopolydimethylsiloxane ofnumber-average molecular weight 2,150, used in Example 28, and 3.15 g ofN-[p-(vinyldimethylsilylmethoxy)-benzoyl]-p-aminophenylN'-[p-(vinyldimethylsilylmethoxy)-benzoyl]-p-aminobenzoate areintroduced into the apparatus described in Example 28.

The contents of the flask are heated to the reflux temperature whilststirring and 3 cm³ of the catalyst solution used in Example 28 are thenadded.

The mixture is kept under these conditions for 5 hours 30 minutes. Afilm is prepared from the reaction solution. This gives a whiteelastomer having a softening point of 160° C, and having an inherentviscosity of 25 cm³ /g, measured as in Example 28.

The percentage composition and the infra-red spectrum correspond tothose of the polymer having the above recurring unit.

EXAMPLES 30 to 33

Following the procedure of Example 23, a series of thermoplasticelastomers is prepared by polyaddition of the4,4'-N,N'-bis-[p-(vinyldimethylsilylmethoxy)-benzoyl]-diaminodiphenylmethane,used in Example 23, with a series ofα,ω-dihydrogenopolydimethylsiloxanes of varying number-average molecularweight; the elastomers obtained contain a plurality of recurring unitsanalogous to that indicated in Example 23.

Films are prepared from the polymers thus obtained, in accordance withthe process described in Example 23, and the mechanical properties andinherent viscosity are determined on these films. The results have beenlisted in the table which follows:

    ______________________________________                                        α,ω-Dihydrogeno-                                                                    Elastomers                                                  polydimethyl-             breaking elonga-                                    siloxane          ν.sub.inh in                                                                       load in  tion at                                    Examples                                                                              --Mn     n        cm.sup.3 /g                                                                         kg/cm.sup.2                                                                          break in %                             ______________________________________                                        30      1,430    17.5     64    115    600                                    31      1,820    22.7     66    88     690                                    32      2,420    31       68    56     730                                    33      2,800    36       77    46     720                                    ______________________________________                                    

We claim:
 1. p-(Dimethylvinylsilylmethoxy)-benzoyl chloride.
 2. Aprocess for the preparation of p-(dimethylvinylsilylmethoxy)-benzoylchloride which comprises reacting dimethylvinylchloromethylsilane with acompound of the formula: ##STR102## in which Z represents a hydrogenatom, an alkali metal or an ammonium group of formula:

    [ (R.sub.9).sub.3 NH--

wherein R₉ represents an alkyl group having from 1 to 4 carbon atoms,with subsequent conversion of the --COOH group into a --COCl group. 3.Process according to claim 2 in which the reactants are brought intocontact at 0° to 150° C, one of the reactants being introduced graduallyinto the reaction mixture.